Procatalyst for polymerization of olefins

ABSTRACT

The present invention relates to a procatalyst comprising the compound represented by Formula (A), preferably the Fischer projection of formula (A) as an internal electron donor. The invention also relates to a process for preparing said procatalyst. Furthermore, the invention is directed to a catalyst system for polymerization of olefins comprising the said procatalyst, a co-catalyst and optionally an external electron donor; a process of making polyolefins by contacting at least one olefin with said catalyst system and to polyolefins obtainable by said process. The invention also relates to the use of said procatalyst in the polymerization of olefins. Moreover, the present invention relates to polymers obtained by polymerization using said procatalyst and to the shaped articles of said polymers.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a 371 of International Application No.PCT/EP2015/062131, filed Jun. 1, 2015, which claims priority to EuropeanApplication No. 15161412.0, filed Mar. 27, 2015, Provisional ApplicationNo. 62/057,262, filed Sep. 30, 2014, and European Application No.14170834.7, filed Jun. 2, 2014, all of which are incorporated byreference in their entirety herein.

The invention relates to a procatalyst for polymerization of olefins.The invention also relates to a process for preparing said procatalystand to the procatalyst obtained via said process. Furthermore, theinvention is directed to a catalyst system for polymerization of olefinscomprising the said procatalyst, a co-catalyst and optionally anexternal electron donor; a process of making polyolefins by contactingat least one olefin with said catalyst system and to polyolefinsobtainable by said process. The invention also relates to the use ofsaid procatalyst in the polymerization of olefins. Moreover, the presentinvention relates to polymers obtained by polymerization using saidprocatalyst and to the shaped articles of said polymers and to the useof said polymers.

Catalyst systems and their components that are suitable for preparing apolyolefin are generally known. One type of such catalysts is generallyreferred to as Ziegler-Natta catalysts. The term “Ziegler-Natta” isknown in the art and it typically refers to catalyst systems comprisinga transition metal-containing solid catalyst compound (also typicallyreferred to as a procatalyst); an organometallic compound (alsotypically referred to as a co-catalyst) and optionally one or moreelectron donor compounds (e.g. external electron donors).

The transition metal-containing solid catalyst compound comprises atransition metal halide (e.g. titanium halide, chromium halide, hafniumhalide, zirconium halide, vanadium halide) supported on a metal ormetalloid compound (e.g. a magnesium compound or a silica compound). Anoverview of such catalyst types is for example given by T. Pullukat andR. Hoff in Catal. Rev.—Sci. Eng. 41, vol. 3 and 4, 389-438, 1999. Thepreparation of such a procatalyst is for example disclosed in WO96/32427A1.

There is, an on-going need in industry for phthalate free catalyst forpreparing polymers.

It is an object of the invention to provide a phthalate free procatalystfor polymerization of olefins. It is a further object of the presentinvention is to provide a procatalyst which shows good performance,especially an improved hydrogen sensitivity.

At least one of the aforementioned objects of the present invention isachieved with a first aspect of the present invention, being aprocatalyst for polymerization of olefins, which comprises the compoundrepresented by formula (A), preferably by the Fischer projection offormula (A), as an internal electron donor,

Each R⁹³ group is independently a linear, branched or cyclic hydrocarbylgroup selected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups,and one or more combinations thereof, preferably having from 1 to 30carbon atoms; preferably wherein each of R⁹³ is independently selectedfrom the group consisting of aryl having 6 to 20 carbon atoms,preferably 6 to 12 carbon atoms. In an embodiment, R⁹³ is preferablyethyl or phenyl, even more preferably ethyl.

R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently selected fromhydrogen or a linear, branched or cyclic hydrocarbyl group, selectedfrom alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or morecombinations thereof, preferably having from 1 to 20 carbon atoms.

Formula A is a so-called carbonate-carbonate compound or dicarbonate orbiscarbonate compound.

In an embodiment of said first aspect, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹are independently selected from a group consisting of hydrogen, C₁-C₁₀straight and branched alkyl; C₃-C₁₀ cycloalkyl; C₆-C₁₀ aryl; and C₇-C₁₀alkaryl and aralkyl group.

In a further embodiment of said first aspect, R⁹⁴ and R⁹⁵ are each ahydrogen atom and R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are independently selected froma group consisting of C₁-C₁₀ straight and branched alkyl; C₃-C₁₀cycloalkyl; C₆-C₁₀ aryl; and C₇-C₁₀ alkaryl and aralkyl group,preferably from C₁-C₁₀ straight and branched alkyl and more preferablyfrom methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl group.

In a further embodiment of said first aspect, when one of R⁹⁶ and R⁹⁷and one of R⁹⁸ and R⁹⁹ has at least one carbon atom, then the other oneof R⁹⁶ and R⁹⁷ and of R⁹⁸ and R⁹⁹ is each a hydrogen atom.

In embodiment, R⁹⁴, R⁹⁵, R⁹⁷, and R⁹⁹ are hydrogen and R⁹⁶, and R⁹⁸ aremethyl. In embodiment, R⁹⁴, R⁹⁵, R⁹⁷, and R⁹⁹ are hydrogen and R⁹⁶, andR⁹⁸ are methyl, and both R⁹³ are phenyl. In embodiment, R⁹⁴, R⁹⁵, R⁹⁷,and R⁹⁹ are hydrogen and R⁹⁶, and R⁹⁸ are methyl, and both R⁹³ areethyl.

In a further embodiment of said first aspect, R⁹³ is a aliphatichydrocarbyl group or an aromatic hydrocarbyl group. R⁹³ may besubstituted on unsubstituted.

In case R⁹³ is an aromatic hydrocarbyl group, it may be phenyl orsubstituted phenyl or any other aromatic group having from 6 to 20carbon atoms.

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and ethyl acetateas activator.

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and ethyl acetate as activator.

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and ethylbenzoate as activator.

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and ethyl benzoate as activator.

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and theprocatalyst is prepared using butyl Grignard, preferably n-BuMgCl, asthe Grignard compound in step i) (see below).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and the procatalyst is prepared using butyl Grignard,preferably n-BuMgCl, as the Grignard compound in step i) (see below).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and theprocatalyst is prepared using phenyl Grignard, preferably PhMgCl, as theGrignard compound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and the procatalyst is prepared using phenyl Grignard,preferably PhMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and ethyl acetateas activator that may be used in step iii) (see below) and theprocatalyst is prepared using butyl Grignard, preferably n-BuMgCl, asthe Grignard compound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and ethyl acetate as activator that may be used in stepiii) (see below) and the procatalyst is prepared using butyl Grignard,preferably n-BuMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and ethyl acetateas activator that may be used in step iii) and the procatalyst isprepared using phenyl Grignard, preferably PhMgCl, as the Grignardcompound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and ethyl acetate as activator that may be used in stepiii) and the procatalyst is prepared using phenyl Grignard, preferablyPhMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and ethylbenzoate as activator that may be used in step iii) and the procatalystis prepared using butyl Grignard, preferably n-BuMgCl, as the Grignardcompound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and ethyl benzoate as activator that may be used in stepiii) and the procatalyst is prepared using butyl Grignard, preferablyn-BuMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by formula A as an internal electron donor and ethylbenzoate as activator that may be used in step iii) and the procatalystis prepared using phenyl Grignard, preferably PhMgCl, as the Grignardcompound in step i).

In a preferred embodiment, the procatalyst comprises the compoundrepresented by the Fischer projection of formula A as an internalelectron donor and ethyl benzoate as activator that may be used in stepiii) and the procatalyst is prepared using phenyl Grignard, preferablyPhMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor andethyl acetate as activator.

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and ethyl acetate as activator.

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor andethyl benzoate as activator.

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and ethyl benzoate as activator.

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor and theprocatalyst is prepared using butyl Grignard, preferably n-BuMgCl, asthe Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and the procatalyst is prepared using butylGrignard, preferably n-BuMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor and theprocatalyst is prepared using phenyl Grignard, preferably PhMgCl, as theGrignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and the procatalyst is prepared using phenylGrignard, preferably PhMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor andethyl acetate as activator that may be used in step iii) and theprocatalyst is prepared using butyl Grignard, preferably n-BuMgCl, asthe Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and ethyl acetate as activator that may be usedin step iii) and the procatalyst is prepared using butyl Grignard,preferably n-BuMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor andethyl acetate as activator that may be used in step iii) and theprocatalyst is prepared using phenyl Grignard, preferably PhMgCl, as theGrignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and ethyl acetate as activator that may be usedin step iii) and the procatalyst is prepared using phenyl Grignard,preferably PhMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor andethyl benzoate as activator that may be used in step iii) and theprocatalyst is prepared using butyl Grignard, preferably n-BuMgCl, asthe Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and ethyl benzoate as activator that may be usedin step iii) and the procatalyst is prepared using butyl Grignard,preferably n-BuMgCl, as the Grignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by formula A as an internal electron donor andethyl benzoate as activator that may be used in step iii) and theprocatalyst is prepared using phenyl Grignard, preferably PhMgCl, as theGrignard compound in step i).

In a preferred embodiment, the procatalyst has been modified by using agroup 13- or transition metal modifier and moreover comprises thecompound represented by the Fischer projection of formula A as aninternal electron donor and ethyl benzoate as activator that may be usedin step iii) and the procatalyst is prepared using phenyl Grignard,preferably PhMgCl, as the Grignard compound in step i).

In a second aspect, the present invention relates to a process forpreparing the procatalyst according to the present invention, comprisingcontacting a magnesium-containing support with a halogen-containingtitanium compound and an internal electron donor, wherein the internalelectron donor is represented by the compound of Formula A, preferablythe Fischer projection of Formula A,

Wherein each R⁹³ group is independently linear, branched or cyclichydrocarbyl a group selected from alkyl, alkenyl, aryl, aralkyl, oralkylaryl groups, and one or more combinations thereof, preferablyhaving from 1 to 30 carbon atoms. In an embodiment, each of R⁹³ isindependently selected from the group consisting of aryl having 6 to 20carbon atoms, preferably 6 to 12 carbon atoms, more preferably phenyl.

R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently selected fromhydrogen or a linear, branched or cyclic hydrocarbyl group, selectedfrom alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, and one or morecombinations thereof, preferably having from 1 to 20 carbon atoms.

In an embodiment of said second aspect, said method comprises the stepsof:

i) contacting a compound R⁴ _(z)MgX⁴ _(2−z) with an alkoxy—oraryloxy-containing silane compound to give a first intermediate reactionproduct, being a solid Mg(OR¹)xX¹ _(2−x), wherein: R⁴ is the same as R¹being a linear, branched or cyclic hydrocarbyl group independentlyselected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylarylgroups, and one or more combinations thereof; wherein said hydrocarbylgroup may be substituted or unsubstituted, may contain one or moreheteroatoms and preferably has from 1 to 20 carbon atoms; X⁴ and X¹ areeach independently selected from the group of consisting of fluoride(F—), chloride (Cl—), bromide (Br—) or iodide (I—), preferably chloride;z is in a range of larger than 0 and smaller than 2, being 0<z<2;

ii) optionally contacting the solid Mg(OR¹)_(x)X¹ _(2−x) obtained instep ii) with at least one activating compound selected from the groupformed by activating electron donors and metal alkoxide compounds offormula M¹(OR²)_(v−w)(OR³)_(w), or M²(OR²)_(v−w) (R³)_(w), to obtain asecond intermediate product; wherein: M¹ is a metal selected from thegroup consisting of Ti, Zr, Hf, Al or Si; v is the valency of M¹; M² isa metal being Si; v is the valency of M²; R² and R³ are each a linear,branched or cyclic hydrocarbyl group independently selected from alkyl,alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one ormore combinations thereof; wherein said hydrocarbyl group may besubstituted or unsubstituted, may contain one or more heteroatoms, andpreferably has from 1 to 20 carbon atoms; v being either 3 or 4; and wis smaller than v; and

iii) contacting the first or second intermediate reaction product,obtained respectively in step i) or ii), with a halogen-containingTi—compound and said internal electron represented by a compound ofFormula A, preferably the Fischer projection of Formula A.

In other words, this embodiment relates to a process comprising thesteps of i) contacting a compound R⁴ _(z)MgX⁴ _(2−z) wherein R⁴ isaromatic, aliphatic or cyclo-aliphatic group containing 1 to 20 carbonatoms, X is a halide, and z is in a range of larger than 0 and smallerthan 2, with an alkoxy- or aryloxy-containing silane compound to give afirst intermediate reaction product; ii) contacting the solidMg(OR¹)_(x)X_(2−x) with at least one activating compound selected fromthe group formed by electron donors and compounds of formulaM¹(OR²)_(v−w) (OR³)_(w), wherein M¹ is Ti, Zr, Hf or Al andM²(OR²)_(v−w) (R³)_(w), wherein M² is Si, each R² and R³, independently,represent an alkyl, alkenyl or aryl group, v is the valency of M, vbeing either 3 or 4 and w is smaller than v; and iii) contacting thesecond intermediate reaction product with a halogen-containingTi-compound, an internal electron donor represented by the Fischerprojection of formula A,

In a further embodiment of said second aspect, during step ii) asactivating compounds an alcohol is used as activating electron donor andtitanium tetraalkoxide is used as metal alkoxide compound.

In a further embodiment, an activator is used, preferably in step iii).

In a further embodiment, said activator is selected from the groupconsisting of benzamides, alkylbenzoates, and mono-esters.

In a further embodiment, said activator is selected from the groupconsisting of ethyl acetate, amyl acetate, butyl acetate, ethylacrylate, methyl methacrylate, and isobutyl methacrylate, benzamide,methylbenzamide, dimethylbenzamide, methylbenzoate, ethylbenzoate,n-propylbenzoate, iso-propylbenzoate, n-butylbenzoate, 2-butylbenzoate,and t-butylbenzoate.

In a preferred embodiment, ethyl acetate is used as activator.

In another aspect a butyl Grignard (preferably BuMgCl) is used toprepare the procatalyst composition. Preferably, an activator is addedduring the preparation of the procatalyst, more preferably ethylacetate.

In an embodiment of said second aspect, said method comprises the stepsof:

i) contacting a BuMgCl compound with tetraethoxysilane to give a firstintermediate reaction product, being a solid Mg(OEt)Cl

ii) contacting the solid Mg(OEt)Cl obtained in step ii) with an alcoholas activating electron donors and titanium tetraalkoxide as metalalkoxide compound

iii) contacting the second intermediate reaction product, obtained instep ii), with a halogen-containing Ti-compound and said internalelectron represented by a compound of Formula A, preferably the Fischerprojection of Formula A.

In another aspect, the present invention relates to a procatalyst forpolymerization of olefins, which comprises the compound represented bythe Fischer projection of formula A as an internal electron donor,wherein: R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are the same or different andare independently selected from a group consisting of hydrogen straight,branched and cyclic alkyl and aromatic substituted and unsubstitutedhydrocarbyl having 1 to 20 carbon atoms; each of R⁹³ is independentlyselected from the group consisting of aryl having 6 to 20 carbon atoms.In an embodiment of said aspect, at least one R⁹³ is phenyl, preferablyboth R⁹³ are phenyl. All other embodiments discussed for the otheraspects of the invention are also applicable to this aspect.

In a specific aspect, the present invention relates to a process forpreparing a procatalyst for polymerization of olefins, comprisingcontacting a magnesium-containing support with a halogen-containingtitanium compound and an internal electron donor, wherein the internalelectron donor is represented by a compound of Formula A, preferably theFischer projection of formula A; wherein: R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, andR⁹⁹ are the same or different and are independently selected from agroup consisting of hydrogen straight, branched and cyclic alkyl andaromatic substituted and unsubstituted hydrocarbyl having 1 to 20 carbonatoms; each R⁹³ group is independently a linear, branched or cyclichydrocarbyl aliphatic or aromatic group selected from alkyl, alkenyl,aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof, preferably having from 1 to 30 carbon atoms;

-   -   said process comprising the steps of:

i) contacting a compound R⁴zMgX⁴ _(2−z) with an alkoxy-oraryloxy-containing silane compound to give a first intermediate reactionproduct, being a solid Mg(OR¹)_(x)X¹ _(2−x), wherein: R⁴ is the same asR¹ being a linear, branched or cyclic hydrocarbyl group independentlyselected from alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylarylgroups, and one or more combinations thereof; wherein said hydrocarbylgroup may be substituted or unsubstituted, may contain one or moreheteroatoms and preferably has from 1 to 20 carbon atoms; X⁴ and X¹ areeach independently selected from the group of consisting of fluoride(F—), chloride (Cl—), bromide (Br—) or iodide (I—), preferably chloride;z is in a range of larger than 0 and smaller than 2, being 0<z<2;

ii) optionally contacting the solid Mg(OR¹)_(x)X¹ _(2−x) obtained instep ii) with at least one activating compound selected from the groupformed by activating electron donors and metal alkoxide compounds offormula M¹(OR²)_(v−w)(OR³)_(w) or M²(OR²)_(v−w)(R³)_(w), to obtain asecond intermediate product; wherein: M¹ is a metal selected from thegroup consisting of Ti, Zr, Hf, Al or Si; v is the valency of M¹; M² isa metal being Si; v is the valency of M²; R² and R³ are each a linear,branched or cyclic hydrocarbyl group independently selected from alkyl,alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one ormore combinations thereof; wherein said hydrocarbyl group may besubstituted or unsubstituted, may contain one or more heteroatoms, andpreferably has from 1 to 20 carbon atoms; v being either 3 or 4 and w issmaller than v; and

iii) contacting the first or second intermediate reaction product,obtained respectively in step i) or ii), with a halogen-containingTi-compound and said internal electron represented by a compound ofFormula A, preferably the Fischer projection of Formula A.

All other embodiments discussed for the other aspects of the inventionare also applicable to this aspect.

In another aspect, the present invention relates to a polymerizationcatalyst system comprising the procatalyst according to the presentinvention, a co-catalyst and optionally an external electron donor.

In another aspect, the present invention relates to a process of makinga polyolefin, preferably a polypropylene, by contacting at least oneolefin with the catalyst system according to the present invention.

In an embodiment of this aspect, propylene is used as said olefin toobtain polypropylene.

In another aspect, the present invention relates to polyolefin,preferably a polypropylene obtainable by the process of making apolyolefin according to the present invention.

In another aspect, the present invention relates to shaped article,comprising the polyolefin, preferably the polypropylene according to theabove aspect of the present invention.

In another aspect, the present invention relates to the use of thecompound represented by Formula A, preferably the Fischer projection ofFormula A, as an internal electron donor in a procatalyst for thepolymerization of at least one olefin,

wherein: each R⁹³ group is independently a linear, branched or cyclichydrocarbyl group preferably having from 1 to 30 carbon atoms. In anembodiment, each of R⁹³ is independently selected from the groupconsisting of aryl having 6 to 20 carbon atoms, preferably 6 to 12carbon atoms, more preferably phenyl.

R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently selected fromhydrogen or a linear, branched or cyclic hydrocarbyl group, selectedfrom alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups,and one or more combinations thereof, preferably having from 1 to 20carbon atoms.

In another aspect, the present invention relates to a compound accordingto Formula A:

wherein each R⁹³ group is independently a linear, branched or cyclichydrocarbyl group preferably having from 1 to 30 carbon atoms.Preferably, each of R⁹³ is independently selected from the groupconsisting of aryl having 6 to 20 carbon atoms, preferably 6 to 12carbon atoms, more preferably phenyl. In another preferred embodiment,R⁹³ is preferably an alkyl, most preferably ethyl.

R⁹⁴, R⁹⁵, R⁹⁶, R⁹′, R⁹⁸, and R⁹⁹ are each independently selected fromhydrogen or a linear, branched or cyclic hydrocarbyl group, selectedfrom alkyl, alkenyl, aryl, aralkyl or alkylaryl groups, and one or morecombinations thereof, preferably having from 1 to 20 carbon atoms.

In an embodiment of this aspect, the compound according to formula A ispentane-2,4-diyl diphenyl dicarbonate:

In an embodiment of this aspect, the compound according to formula A isdiethyl pentane-2,4-diyl dicarbonate:

These aspects and embodiments will be described in more detail below.

The following definitions are used in the present description and claimsto define the stated subject matter. Other terms not cited below aremeant to have the generally accepted meaning in the field.

For the all aspects of the present invention, the following is observed:

“Ziegler-Natta catalyst” as used in the present description means: atransition metal-containing solid catalyst compound comprises atransition metal halide selected from titanium halide, chromium halide,hafnium halide, zirconium halide, and vanadium halide, supported on ametal or metalloid compound (e.g. a magnesium compound or a silicacompound).

“Ziegler-Natta catalytic species” or “catalytic species” as used in thepresent description means: a transition metal-containing speciescomprises a transition metal halide selected from titanium halide,chromium halide, hafnium halide, zirconium halide and vanadium halide,

“internal donor” or “internal electron donor” or “ID” as used in thepresent description means: an electron-donating compound containing oneor more atoms of oxygen (O) and/or nitrogen (N). This ID is used as areactant in the preparation of a solid procatalyst. An internal donor iscommonly described in prior art for the preparation of a solid-supportedZiegler-Natta catalyst system for olefins polymerization; i.e. bycontacting a magnesium-containing support with a halogen-containing Ticompound and an internal donor.

“external donor” or “external electron donor” or “ED” as used in thepresent description means: an electron-donating compound used as areactant in the polymerisation of olefins. An ED is a compound addedindependent of the procatalyst. It is not added during procatalystformation. It contains at least one functional group that is capable ofdonating at least one pair of electrons to a metal atom. The ED mayinfluence catalyst properties, non-limiting examples thereof areaffecting the stereoselectivity of the catalyst system in polymerizationof olefins having 3 or more carbon atoms, hydrogen sensitivity, ethylenesensitivity, randomness of co-monomer incorporation and catalystproductivity.

“activator” as used in the present description means: anelectron-donating compound containing one or more atoms of oxygen (O)and/or nitrogen (N) which is used to during the synthesis of theprocatalyst prior to or simultaneous with the addition of an internaldonor.

“activating compound” as used in the present description means: acompound used to activate the solid support prior to contacting it withthe catalytic species.

“modifier” or “Group 13- or transition metal modifier” as used in thepresent description means: a metal modifier comprising a metal selectedfrom the metals of Group 13 of the IUPAC Periodic Table of elements andtransition metals. Where in the description the terms metal modifier ormetal-based modifier is used, Group 13- or transition metal modifier ismeant.

“procatalyst” and “catalyst component” as used in the presentdescription have the same meaning: a component of a catalyst compositiongenerally comprising a solid support, a transition metal-containingcatalytic species and optionally one or more internal donor.

“halide” or “halogen” as used in the present description means: an ionselected from the group of: fluoride (F—), chloride (Cl—), bromide (Br—)or iodide (I—).

“Heteroatom” as used in the present description means: an atom otherthan carbon or hydrogen, preferably F, Cl, Br, I, N, O, P, B, S or Si.

“heteroatom selected from group 13, 14, 15, 16 or 17 of the IUPACPeriodic Table of the Elements” as used in the present descriptionmeans: a hetero atom selected from B, Al, Ga, In, TI [Group 13], Si, Ge,Sn, Pb [Group 14], N, P, As, Sb, Bi [Group 15], S, Se, Te, Po [Group16], F, Cl, Br, I, At [Group 17]. More preferably,” heteroatom selectedfrom group 13, 14, 15, 16 or 17 of the IUPAC Periodic Table of theElements” includes N, O, P, B, S, or Si.

“hydrocarbyl” as used in the present description means: is a substituentcontaining hydrogen and carbon atoms, or linear, branched or cyclicsaturated or unsaturated aliphatic radical, such as alkyl, alkenyl,alkadienyl and alkynyl; alicyclic radical, such as cycloalkyl,cycloalkadienyl cycloalkenyl; aromatic radical, such as monocyclic orpolycyclic aromatic radical, as well as combinations thereof, such asalkaryl and aralkyl.

“substituted hydrocarbyl” as used in the present description means: is ahydrocarbyl group that is substituted with one or more non-hydrocarbylsubstituent groups. A non-limiting example of a non-hydrocarbylsubstituent is a heteroatom. Examples are alkoxycarbonyl (viz.carboxylate) groups. When in the present description “hydrocarbyl” isused it can also be “substituted hydrocarbyl”, unless stated otherwise.

“alkyl” as used in the present description means: an alkyl group being afunctional group or side-chain consisting of carbon and hydrogen atomshaving only single bonds. An alkyl group may be straight or branched andmay be un-substituted or substituted.

“aryl” as used in the present description means: an aryl group being afunctional group or side-chain derived from an aromatic ring. An arylgroup and may be un-substituted or substituted with straight or branchedhydrocarbyl groups. An aryl group also encloses alkaryl groups whereinone or more hydrogen atoms on the aromatic ring have been replaced byalkyl groups.

“aralkyl” as used in the present description means: an arylalkyl groupbeing an alkyl group wherein one or more hydrogen atoms have beenreplaced by aryl groups “alkoxide” or “alkoxy” as used in the presentdescription means: a functional group or side-chain obtained from aalkyl alcohol. It consist of an alkyl bonded to a negatively chargedoxygen atom.

“aryloxide” or “aryloxy” or “phenoxide” as used in the presentdescription means: a functional group or side-chain obtained from anaryl alcohol. It consist of an aryl bonded to a negatively chargedoxygen atom.

“Grignard reagent” or “Grignard compound” as used in the presentdescription means: a compound or a mixture of compounds of formula R⁴_(z)MgX⁴ _(2−z) (R⁴, z, and X⁴ are as defined below) or it may be acomplex having more Mg clusters, e.g. R₄Mg₃Cl₂.

“polymer” as used in the present description means: a chemical compoundcomprising repeating structural units, wherein the structural units aremonomers.

“olefin” as used in the present description means: an alkene.

“olefin-based polymer” or “polyolefin” as used in the presentdescription means: a polymer of one or more alkenes.

“propylene-based polymer” as used in the present description means: apolymer of propylene and optionally a comonomer. “polypropylene” as usedin the present description means: a polymer of propylene.

“copolymer” as used in the present description means: a polymer preparedfrom two or more different monomers.

“monomer” as used in the present description means: a chemical compoundthat can undergo polymerization.

“thermoplastic” as used in the present description means: capable ofsoftening or fusing when heated and of hardening again when cooled.

“Polymer composition” as used in the present description means: amixture of either two or more polymers or of one or more polymers andone or more additives.

“MWD” or “Molecular weight distribution” as used in the presentdescription means: the same as “PDI” or “polydispersity index”. It isthe ratio of the weight-average molecular weight (Mw) to the numberaverage molecular weight (Mn), viz. Mw/Mn, and is used as a measure ofthe broadness of molecular weight distribution of a polymer. Mw and Mnare determined by GPC using either: i) a Waters 150° C. gel permeationchromatograph combined with a Viscotek 100 differential viscosimeter;the chromatograms were run at 140° C. using 1,2,4-trichlorobenzene as asolvent; the refractive index detector was used to collect the signalfor molecular weights; or ii) Polymer Laboratories PL-GPC220 combinedwith a Polymer Laboratories PL BV-400 viscomsimeter, and a refractiveindex detector, and a Polymer Char IR5 infrared detected; thechromatograms were run at 150° C. using 1,2,4-trichlorobenzene as asolvent; the refractive index detector was used to collect the signalfor molecular weights. The values for both methods are the same sincethey both use calibration against standards.

“XS” or “xylene soluble fraction” or “CXS” or “cold soluble xylenefraction” as used in the present description means: the weightpercentage (wt. %) of soluble xylene in the isolated polymer, measuredaccording to ASTM D 5492-10.

“polymerization conditions” as used in the present description means:temperature and pressure parameters within a polymerization reactorsuitable for promoting polymerization between the procatalyst and anolefin to form the desired polymer. These conditions depend on the typeof polymerization used.

“production rate” or “yield” as used in the present description means:the amount of kilograms of polymer produced per gram of procatalystconsumed in the polymerization reactor per hour, unless statedotherwise.

“APP wt. %” or “weight percentage of atactic polypropylene” as used inthe present description means: the fraction of polypropylene obtained ina slurry polymerization that is retained in the solvent. APP can bedetermined by taking 100 ml of the filtrate (“y” in millilitres)obtained during separation from polypropylene powder after slurrypolymerization (“x” in grammes). The solvent is dried over a steam bathand then under vacuum at 60° C. That yields APP (“z” in grammes). Thetotal amount of APP (“q” in grammes) is (y/100)*z. The weight percentageof APP is (q/q+x))*100%.

“MFR” or “Melt Flow rate” as used in the present description is measuredat a temperature of 230° C. with 2.16 kg load and measured according toISO 1133:2005.

Unless stated otherwise, when it is stated that any R group is“independently selected from” this means that when several of the same Rgroups are present in a molecule they may have the same meaning of theymay not have the same meaning. For example, for the compound R₂M,wherein R is independently selected from ethyl or methyl, both R groupsmay be ethyl, both R groups may be methyl or one R group may be ethyland the other R group may be methyl.

The present invention is described below in more detail. All embodimentsdescribed with respect to one aspect of the present invention are alsoapplicable to the other aspects of the invention, unless otherwisestated.

It has been surprisingly found out that the procatalyst comprising thecompound of formula A as an internal electron donor shows good controlof stereochemistry and shows a good hydrogen sensitivity.

Polyolefins having medium molecular weight distribution are hereinpolyolefins that may have a Mw/Mn between 4.5 and 6.5, for examplebetween 5.5 and 6.0.

The high isotacticity indicates low amount of amorphous atactic polymerin the products obtained, such as for example lower than 3 wt. %, lowerthan 2 wt. % or even lower than 1 wt. % of the total amount of polymer.

The xylene solubles content of the polyolefins obtained with theprocatalyst according to the present invention is moderate to low, forinstance lower than 12 wt % or lower than 10 wt %, lower than 8 wt % andor lower than 4 wt %.

The methods used in the present invention to determine the molecularweight distribution, the amount of atactic polymer, the xylene solublescontent and melt flow range are described in the experimental part ofthe present invention.

A further advantage of the present invention is that a reasonably lowamount of wax is formed, i.e. low molecular weight polymers during thepolymerization reaction, which results in reduced or no “stickiness” onthe inside walls of the polymerization reactor and inside the reactor.In addition, the procatalyst according to the present invention can bephthalate-free and thus allows obtaining non-toxic polyolefins showingno harmful effects on human health and which thus can be used forinstance in food and medical industry.

Preferably, the procatalyst according to the invention comprises thecompound having formula A as the only internal electron donor in aZiegler-Natta catalyst composition.

Embodiments of the internal donor are disclosed below

R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each independently selected fromhydrogen or a hydrocarbyl group, selected from alkyl, alkenyl, aryl,aralkyl or alkylaryl groups, and one or more combinations thereof. Saidhydrocarbyl group may be linear, branched or cyclic. Said hydrocarbylgroup may be substituted or unsubstituted. Said hydrocarbyl group maycontain one or more heteroatoms. Preferably, said hydrocarbyl group hasfrom 1 to 20 carbon atoms.

More preferably, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are independentlyselected from a group consisting of hydrogen, C₁-C₁₀ straight andbranched alkyl; C₃-C₁₀ cycloalkyl; C₆-C₁₀ aryl; and C₇-C₁₀ alkaryl andaralkyl group.

Even more preferably, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are independentlyselected from a group consisting of hydrogen, methyl, ethyl, propyl,isopropyl, butyl, tert-butyl, phenyl, trifluoromethyl and halophenylgroup.

Most preferably, R⁹⁴, R⁹⁵, R⁹⁶, R⁹⁷, R⁹⁸, and R⁹⁹ are each hydrogen,methyl, ethyl, propyl, tert-butyl, phenyl or trifluoromethyl.

Preferably, R⁹⁴ and R⁹⁵ is each a hydrogen atom.

More preferably, R⁹⁴ and R⁹⁵ is each a hydrogen atom and each of R⁹⁶,R⁹⁷, R⁹⁸, and R⁹⁹ is selected from the group consisting of hydrogen,C₁-C₁₀ straight and branched alkyls; C₃-C₁₀ cycloalkyls; C₆-C₁₀ aryls;and C₇-C₁₀ alkaryl and aralkyl group.

Preferably, at least one of R⁹⁶ and R⁹⁷ and at least one of R⁹⁸ and R⁹⁹is a hydrocarbyl group.

More preferably, when at least one of R⁹⁶ and R⁹⁷ and one of R⁹⁸ and R⁹⁹is a hydrocarbyl group having at least one carbon atom then the otherone of R⁹⁶ and R⁹⁷ and one of R⁹⁸ and R⁹⁹ is each a hydrogen atom. R⁹⁷and R⁹⁹ may be selected from the group consisting of C₁-C₁₀ alkyl, suchas methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, phenyl,trifluoromethyl and halophenyl group; and most preferably methyl.

Most preferably, when one of R⁹⁶ and R⁹⁷and one of R⁹⁸ and R⁹⁹ is ahydrocarbyl group having at least one carbon atom (preferably methyl),then the other one of R⁹⁶ and R⁹⁷ and of R⁹⁸ and R⁹⁹ is each a hydrogenatom and R⁹⁴ and R⁹⁵ is each a hydrogen atom.

The compound according to Formula A can be made by any method known inthe art.

The molar ratio of the internal donor of Formula A relative to themagnesium can be from 0.02 to 0.5. Preferably, this molar ratio is from0.05 to 0.2.

The process for preparing the procatalyst according to the presentinvention comprises contacting a magnesium-containing support with ahalogen-containing titanium compound and an internal donor, wherein theinternal electron donor is the compound represented by Formula A,preferably the Fischer projection of the Formula A.

The present invention is related to Ziegler-Natta type catalyst. AZiegler-Natta type procatalyst generally comprising a solid support, atransition metal-containing catalytic species and an internal donor. Thepresent invention moreover relates to a catalyst system comprising aZiegler-Natta type procatalyst, a co-catalyst and optionally an externalelectron donor.

The transition metal-containing solid catalyst compound comprises atransition metal halide (e.g. titanium halide, chromium halide, hafniumhalide, zirconium halide, vanadium halide) supported on a metal ormetalloid compound (e.g. a magnesium compound or a silica compound).

Specific examples of several types of Ziegler-Natta catalyst asdisclosed below.

Preferably, the present invention is related to a so-called TiNocatalyst. It is a magnesium-based supported titanium halide catalystoptionally comprising an internal donor.

The magnesium-containing support and halogen-containing titaniumcompounds used in the process according to the present invention areknown in the art as typical components of a Ziegler-Natta catalystcomposition. Any of said Ziegler-Natta catalytic species known in theart can be used in the process according to the present invention. Forinstance, synthesis of such titanium-magnesium based catalystcompositions with different magnesium-containing support-precursors,such as magnesium halides, magnesium alkyls and magnesium aryls, andalso magnesium alkoxy and magnesium aryloxy compounds for polyolefinproduction, particularly of polypropylenes production are described forinstance in U.S. Pat. No. 4,978,648, WO96/32427A1, WO01/23441 A1, EP1283222A1, EP1222 21461; U.S. Pat. Nos. 5,077,357; 5,556,820; 4,414,132;5,106,806 and 5,077,357 but the present process is not limited to thedisclosure in these documents.

EP 1 273 595 of Borealis Technology discloses a process for producing anolefin polymerisation procatalyst in the form of particles having apredetermined size range, said process comprising: preparing a solutiona complex of a group Ila metal and an electron donor by reacting acompound of said metal with said electron donor or a precursor thereofin an organic liquid reaction medium; reacting said complex, insolution, with at least one compound of a transition metal to produce anemulsion the dispersed phase of which contains more than 50 mol % of thegroup Ila metal in said complex; maintaining the particles of saiddispersed phase within the average size range 10 to 200 mu m byagitation in the presence of an emulsion stabilizer and solidifying saidparticles; and recovering, washing and drying said particles to obtainsaid procatalyst.

EP 0 019 330 of Dow discloses a Ziegler-Natta type catalyst composition.Said olefin polymerization catalyst composition comprising: a) areaction product of an organo aluminum compound and an electron donor,and b) a solid component which has been obtained by halogenating amagnesium compound with the formula MgR¹R² wherein R¹ is an alkyl, aryl,alkoxide or aryloxide group and R² is an alkyl, aryl, alkoxide oraryloxide group or halogen, with a halide of tetravalent titanium in thepresence of a halohydrocarbon, and contacting the halogenated productwith a tetravalent titanium compound.

The procatalyst may be produced by any method known in the art using thepresent internal electron donor according for Formula A.

The procatalyst may also be produced as disclosed in WO96/32426A; thisdocument discloses a process for the polymerization of propylene using acatalyst comprising a procatalyst obtained by a process wherein acompound with formula Mg(OAlk)_(x)Cl_(y) wherein x is larger than 0 andsmaller than 2, y equals 2-x and each Alk, independently, represents analkyl group, is contacted with a titanium tetraalkoxide and/or analcohol in the presence of an inert dispersant to give an intermediatereaction product and wherein the intermediate reaction product iscontacted with titanium tetrachloride in the presence of an internaldonor, which is di-n-butyl phthalate.

Preferably, the Ziegler-Natta type procatalyst in the catalyst systemaccording to the present invention is obtained by the process asdescribed in WO 2007/134851 A1. In Example I the process is disclosed inmore detail. Example I including all sub-examples (IA-IE) isincorporated into the present description. More details about thedifferent embodiments are disclosed starting on page 3, line 29 to page14 line 29. These embodiments are incorporated by reference into thepresent description.

In the following part of the description the different steps and phasesof the process for preparing the procatalyst according to the presentinvention will be discussed.

The process for preparing a procatalyst according to the presentinvention comprises the following phases:

-   -   Phase A): preparing a solid support for the procatalyst;    -   Phase B): optionally activating said solid support obtained in        phase A) using one or more activating compounds to obtain an        activated solid support;    -   Phase C): contacting said solid support obtained in phase A) or        said activated solid support in phase B) with a catalytic        species wherein phase C) comprises one of the following:        -   contacting said solid support obtained in phase A) or said            activated solid support in phase B) with a catalytic species            and one or more internal donors to obtain said procatalyst;            or        -   contacting said solid support obtained in phase A) or said            activated solid support in phase B) with a catalytic species            and one or more internal donors to obtain an intermediate            product; or        -   contacting said solid support obtained in phase A) or said            activated solid support in phase B) with a catalytic species            and an activator to obtain an intermediate product;    -   optionally Phase D: modifying said intermediate product obtained        in phase C) wherein phase D) comprises on of the following:        -   modifying said intermediate product obtained in phase C)            with a Group 13- or transition metal modifier in case an            internal donor was used during phase C), in order to obtain            a procatalyst;        -   modifying said intermediate product obtained in phase C)            with a Group 13- or transition metal modifier and an            internal donor in case an activator was used during phase            C), in order to obtain a procatalyst.

The procatalyst thus prepared can be used in polymerization of olefinsusing an external donor and a co-catalyst.

It is thus noted that the process according to the present invention isdifferent from the prior art process by the use of a different internaldonor.

The various steps used to prepare the procatalyst according to thepresent invention (and the prior art) are described in more detailbelow.

Phase A: Preparing a Solid Support for the Catalyst.

In the process of the present invention preferably amagnesium-containing support is used. Said magnesium-containing supportis known in the art as a typical component of a Ziegler-Nattaprocatalyst. This step of preparing a solid support for the catalyst isthe same as in the prior art process. The following description explainsthe process of preparing magnesium-based support. Other supports may beused.

Synthesis of magnesium-containing supports, such as magnesium halides,magnesium alkyls and magnesium aryls, and also magnesium alkoxy andmagnesium aryloxy compounds for polyolefin production, particularly ofpolypropylenes production are described for instance in U.S. Pat. No.4,978,648, WO96/32427A1, WO01/23441 Al, EP1283 222A1, EP1222 21461; U.S.Pat. Nos. 5,077,357; 5,556,820; 4,414,132; 5,106,806 and 5,077,357 butthe present process is not limited to the disclosure in these documents.

Preferably, the process for preparing the solid support for theprocatalyst according to the present invention comprises the followingsteps: step o) which is optional and step i). Step o) preparation of theGrignard reagent (optional) and Step i) reacting a Grignard compoundwith a silane compound.

Step o) Preparation of the Grignard Reagent (Optional).

A Grignard reagent, R⁴zMgX⁴ _(2−z) used in step i) may be prepared bycontacting metallic magnesium with an organic halide R⁴X⁴, as describedin WO 96/32427 A1 and WO01/23441 A1. All forms of metallic magnesium maybe used, but preferably use is made of finely divided metallicmagnesium, for example magnesium powder. To obtain a fast reaction it ispreferable to heat the magnesium under nitrogen prior to use.

R⁴ is a hydrocarbyl group independently selected from alkyl, alkenyl,aryl, aralkyl, alkylaryl, or alkoxycarbonyl groups, wherein saidhydrocarbyl group may be linear, branched or cyclic, and may besubstituted or unsubstituted; said hydrocarbyl group preferably havingfrom 1 to 20 carbon atoms or combinations thereof. The R⁴ group maycontain one or more heteroatoms.

X⁴ is selected from the group of consisting of fluoride (F—), chloride(Cl—), bromide (Br—) or iodide (I—). The value for z is in a range oflarger than 0 and smaller than 2: 0<z<2

Combinations of two or more organic halides R⁴X⁴ can also be used.

The magnesium and the organic halide R⁴X⁴ can be reacted with each otherwithout the use of a separate dispersant; the organic halide R⁴X⁴ isthen used in excess.

The organic halide R⁴X⁴ and the magnesium can also be brought intocontact with one another and an inert dispersant. Examples of thesedispersants are: aliphatic, alicyclic or aromatic dispersants containingfrom 4 up to 20 carbon atoms.

Preferably, in this step o) of preparing R⁴ _(z)MgX⁴ _(2−z), also anether is added to the reaction mixture. Examples of ethers are: diethylether, diisopropyl ether, dibutyl ether, diisobutyl ether, diisoamylether, diallyl ether, tetrahydrofuran and anisole. Dibutyl ether and/ordiisoamyl ether are preferably used. Preferably, an excess ofchlorobenzene is used as the organic halide R⁴X⁴. Thus, thechlorobenzene serves as dispersant as well as organic halide R⁴X⁴.

The organic halide/ether ratio acts upon the activity of theprocatalyst. The chlorobenzene/dibutyl ether volume ratio may forexample vary from 75:25 to 35:65, preferably from 70:30 to 50:50.

Small amounts of iodine and/or alkyl halides can be added to cause thereaction between the metallic magnesium and the organic halide R⁴X⁴ toproceed at a higher rate. Examples of alkyl halides are butyl chloride,butyl bromide and 1,2-dibromoethane. When the organic halide R⁴X⁴ is analkyl halide, iodine and 1,2-dibromoethane are preferably used.

The reaction temperature for step o) of preparing R⁴ _(z)MgX⁴ _(2−z)normally is from 20 to 150° C.; the reaction time is normally from 0.5to 20 hours. After the reaction for preparing R⁴ _(z)MgX⁴ _(2−z) iscompleted, the dissolved reaction product may be separated from thesolid residual products. The reaction may be mixed. The stirring speedcan be determined by a person skilled in the art and should besufficient to agitate the reactants.

Step i) Reacting a Grignard Compound with a Silane Compound.

Step i): contacting a compound R⁴ _(z)MgX⁴ _(2−z)—wherein R₄, X⁴, and zare as discussed herein—with an alkoxy- or aryloxy-containing silanecompound to give a first intermediate reaction product. Said firstintermediate reaction product is a solid magnesium-containing support.

In step i) a first intermediate reaction product is thus prepared bycontacting the following reactants: * a Grignard reagent—being acompound or a mixture of compounds of formula R⁴ _(z)MgX⁴ _(2−z) and *an alkoxy- or aryloxy-containing silane compound. Examples of thesereactants are disclosed for example in WO 96/32427 A1 and WO01/23441 A1.

The compound R⁴ _(z)MgX⁴ _(2−z) used as starting product is alsoreferred to as a Grignard compound. In R⁴ _(z)MgX⁴ _(2−z), X⁴ ispreferably chlorine or bromine, more preferably chlorine.

R⁴ can be an alkyl, aryl, aralkyl, alkoxide, phenoxide, etc., ormixtures thereof. Suitable examples of group R⁴ are methyl, ethyl,n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, hexyl, cyclohexyl, octyl,phenyl, tolyl, xylyl, mesityl, benzyl, phenyl, naphthyl, thienyl,indolyl. In a preferred embodiment of the invention, R⁴ represents anaromatic group, for instance a phenyl group.

Preferably, as Grignard compound R⁴ _(z)MgX⁴ _(2−z) used in step i) aphenyl Grignard or a butyl Grignard is used. The selection for eitherthe phenyl Grignard or the butyl Grignard depends on the requirements.

When Grignard compound is used, a compound according to the formula R⁴_(z)MgX⁴ _(2−z) is meant. When phenyl Grignard is used a compoundaccording to the formula R⁴ _(z)MgX⁴ _(2−z) wherein R⁴ is phenyl, e.g.PhMgCl, is meant. When butyl Grignard is used, a compound according tothe formula R⁴ _(z)MgX⁴ _(2−z) wherein R⁴ is butyl, e.g. BuMgCl orn-BuMgCl, is meant.

An advantage of the use of phenyl Grignard are that it is more activethat butyl Grignard. Preferably, when butyl Grignard is used, anactivation step using an aliphatic alcohol, such as methanol is carriedout in order to increase the activity. Such an activation step may notbe required with the use of phenyl Grignard. A disadvantage of the useof phenyl Grignard is that benzene rest products may be present and thatit is more expensive and hence commercially less interesting.

An advantage of the use of butyl Grignard is that it is benzene free andis commercially more interesting due to the lower price. A disadvantageof the use of butyl Grignard is that in order to have a high activity,an activation step is required.

The process to prepare the procatalyst according to the presentinvention can be carried out using any Grignard compound, but the twostated above are the two that are most preferred.

In the Grignard compound of formula R⁴ _(z)MgX⁴ _(2−z) z is preferablyfrom about 0.5 to 1.5.

The compound R⁴ ₂MgX⁴ _(2−z) may be prepared in an optional step (stepo) which is discussed above), preceding step i) or may be obtained froma different process.

It is explicitly noted that it is possible that the Grignard compoundused in step i) may alternatively have a different structure, forexample, may be a complex. Such complexes are already known to theskilled person in the art; a particular example of such complexes isPhenyl₄Mg₃Cl₂.

The alkoxy-or aryloxy-containing silane used in step i) is preferably acompound or a mixture of compounds with the general formula Si(OR⁵)_(4−n)R⁶n, wherein:

It should be noted that the R⁵ group is the same as the R¹ group. The R¹group originates from the R⁵ group during the synthesis of the firstintermediate reaction product.

R⁵ is a hydrocarbyl group independently selected from alkyl, alkenyl,aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be linear, branched orcyclic. Said hydrocarbyl group may be substituted or unsubstituted. Saidhydrocarbyl group may contain one or more heteroatoms. Preferably, saidhydrocarbyl group has from 1 to 20 carbon atoms, more preferably from 1to 12 carbon atoms, even more preferably from 1 to 6 carbon atoms.Preferably, said hydrocarbyl group is an alkyl group, preferably havingfrom 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms,even more preferably from 1 to 6 carbon atoms, such as for examplemethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl,tert-butyl, pentyl or hexyl; most preferably, selected from ethyl andmethyl.

R⁶ is a hydrocarbyl group independently selected from alkyl, alkenyl,aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be linear, branched orcyclic. Said hydrocarbyl group may be substituted or unsubstituted. Saidhydrocarbyl group may contain one or more heteroatoms. Preferably, saidhydrocarbyl group has from 1 to 20 carbon atoms, more preferably from 1to 12 carbon atoms, even more preferably from 1 to 6 carbon atoms.Preferably, said hydrocarbyl group is an alkyl group, preferably havingfrom 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms,even more preferably from 1 to 6 carbon atoms, such as for examplemethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl,tert-butyl, or cyclopentyl.

The value for n is in the range of 0 up to 3, preferably n is from 0 upto and including 1.

Examples of suitable silane-compounds include tetramethoxysilane,tetraethoxysilane, methyltrimethoxysilane, methyltributoxysilane,phenyltriethoxy-silane, diethyldiphenoxysilane, n-propyltriethoxysilane,diisopropyldi-methoxysilane, diisobutyldimethoxysilane,n-propyltrimethoxysilane, cyclohexyl-methyldimethoxysilane,dicyclopentyldimethoxy-silane, isobutylisopropyldimethoxyl-silane,phenyl-trimethoxysilane, diphenyl-dimethoxysilane,trifluoropropylmethyl-dimethoxysilane,bis(perhydroisoquinolino)-dimethoxysilane, dicyclohexyldimethoxy-silane,dinorbornyl-dimethoxysilane, di(n-propyl)dimethoxysilane,di(iso-propyl)-dimethoxysilane, di(n-butyl)dimethoxysilane and/ordi(iso-butyl)dimethoxysilane.

Preferably, tetraethoxy-silane is used as silane-compound in preparingthe solid Mg-containing compound during step i) in the process accordingto the present invention.

Preferably, in step i) the silane-compound and the Grignard compound areintroduced simultaneously to a mixing device to result in particles ofthe first intermediate reaction product having advantageous morphology.This is for example described in WO 01/23441 A1. Here, ‘morphology’ doesnot only refer to the shape of the particles of the solid Mg-compoundand the catalyst made therefrom, but also to the particle sizedistribution (also characterized as span), its fines content, powderflowability, and the bulk density of the catalyst particles. Moreover,it is well known that a polyolefin powder produced in polymerizationprocess using a catalyst system based on such procatalyst has a similarmorphology as the procatalyst (the so-called “replica effect”; see forinstance S. van der Ven, Polypropylene and other Polyolefins, Elsevier1990, p. 8-10). Accordingly, almost round polymer particles are obtainedwith a length/diameter ratio (I/D) smaller than 2 and with good powderflowability.

As discussed above, the reactants are preferably introducedsimultaneously. With “introduced simultaneously” is meant that theintroduction of the Grignard compound and the silane-compound is done insuch way that the molar ratio Mg/Si does not substantially vary duringthe introduction of these compounds to the mixing device, as describedin WO 01/23441 A1.

The silane-compound and Grignard compound can be continuously orbatch-wise introduced to the mixing device. Preferably, both compoundsare introduced continuously to a mixing device.

The mixing device can have various forms; it can be a mixing device inwhich the silane-compound is premixed with the Grignard compound, themixing device can also be a stirred reactor, in which the reactionbetween the compounds takes place. The separate components may be dosedto the mixing device by means of peristaltic pumps.

Preferably, the compounds are premixed before the mixture is introducedto the reactor for step i). In this way, a procatalyst is formed with amorphology that leads to polymer particles with the best morphology(high bulk density, narrow particle size distribution, (virtually) nofines, excellent flowability).

The Si/Mg molar ratio during step i) may range from 0.2 to 20.Preferably, the Si/Mg molar ratio is from 0.4 to 1.0.

The period of premixing of the reactants in above indicated reactionstep may vary between wide limits, for instance 0.1 to 300 seconds.Preferably, premixing is performed during 1 to 50 seconds.

The temperature during the premixing step of the reactants is notspecifically critical, and may for instance range from 0 to 80° C.;preferably the temperature is from 10° C. to 50° C.

The reaction between said reactants may, for instance, take place at atemperature from −20° C. to 100° C.; for example at a temperature offrom 0° C. to 80° C. The reaction time is for example from 1 to 5 hours.

The mixing speed during the reaction depends on the type of reactor usedand the scale of the reactor used. The mixing speed can be determined bya person skilled in the art. As a non-limiting example, mixing may becarried out at a mixing speed of from 250 to 300 rpm. In an embodiment,when a blade stirrer is used the mixing speed is from 220 to 280 rpm andwhen a propeller stirrer is used the mixing speed is from 270 to 330rpm. The stirrer speed may be increased during the reaction. Forexample, during the dosing, the speed of stirring may be increased everyhour by 20-30 rpm.

Preferably, PhMgCl or n-BuMgCl is the Grignard agent used in step i).

The first intermediate reaction product obtained from the reactionbetween the silane compound and the Grignard compound is usuallypurified by decanting or filtration followed by rinsing with an inertsolvent, for instance a hydrocarbon solvent with for example 1-20 carbonatoms, like pentane, iso-pentane, hexane or heptane. The solid productcan be stored and further used as a suspension in said inert solvent.Alternatively, the product may be dried, preferably partly dried, andpreferably under mild conditions; e.g. at ambient temperature andpressure.

The first intermediate reaction product obtained by this step i) maycomprise a compound of the formula Mg(OR¹)_(x)X¹ _(2−x), wherein:

R¹ is a hydrocarbyl group independently selected from alkyl, alkenyl,aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be linear, branched orcyclic. Said hydrocarbyl group may be substituted or unsubstituted. Saidhydrocarbyl group may contain one or more heteroatoms. Preferably, saidhydrocarbyl group has from 1 to 20 carbon atoms, more preferably from 1to 12 carbon atoms, even more preferably from 1 to 6 carbon atoms.Preferably, said hydrocarbyl group is an alkyl group, preferably havingfrom 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms,even more preferably from 1 to 6 carbon atoms. Most preferably selectedfrom ethyl and methyl.

X¹ is selected from the group of consisting of fluoride (F—), chloride(Cl—), bromide (Br—) or iodide (I—). Preferably, X¹ is chloride orbromine and more preferably, X¹ is chloride.

The value for x is in the range of larger than 0 and smaller than 2:0<z<2. The value for x is preferably from 0.5 to 1.5.

Phase B: Activating said Solid Support for the Catalyst.

This step of activating said solid support for the catalyst is anoptional step that is not required, but is preferred, in the presentinvention. If this step of activation is carried out, preferably, theprocess for activating said solid support comprises the following stepii). This phase may comprise one or more stages.

Step ii) Activation of the Solid Magnesium Compound.

Step ii): contacting the solid Mg(OR¹)_(x)X¹ _(2−x) with at least oneactivating compound selected from the group formed by activatingelectron donors and metal alkoxide compounds of formulaM¹(OR²)_(v−w)(OR³)_(w) or M ²(OR²)_(v−w)(R³)_(w), wherein:

R² is a hydrocarbyl group independently selected from alkyl, alkenyl,aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be linear, branched orcyclic. Said hydrocarbyl group may be substituted or unsubstituted. Saidhydrocarbyl group may contain one or more heteroatoms. Preferably, saidhydrocarbyl group has from 1 to 20 carbon atoms, more preferably from 1to 12 carbon atoms, even more preferably from 1 to 6 carbon atoms.Preferably, said hydrocarbyl group is an alkyl group, preferably havingfrom 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms,even more preferably from 1 to 6 carbon atoms, such as for examplemethyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl,tert-butyl, pentyl or hexyl; most preferably selected from ethyl andmethyl.

R³ is a hydrocarbyl group independently selected from alkyl, alkenyl,aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be linear, branched orcyclic. Said hydrocarbyl group may be substituted or unsubstituted. Saidhydrocarbyl group may contain one or more heteroatoms. Preferably, saidhydrocarbyl group has from 1 to 20 carbon atoms, more preferably from 1to 12 carbon atoms, even more preferably from 1 to 6 carbon atoms.Preferably, said hydrocarbyl group is an alkyl group, preferably havingfrom 1 to 20 carbon atoms, more preferably from 1 to 12 carbon atoms,even more preferably from 1 to 6 carbon atoms; most preferably selectedfrom methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, iso-butyl,tert-butyl, and cyclopentyl.

M¹ is a metal selected from the group consisting of Ti, Zr, Hf, Al orSi; v is the valency of M¹; M² is a metal being Si; v is the valency ofM² and v being either 3 or 4 and w is smaller than v.

The electron donors and the compounds of formulaM¹(OR²)_(v−w)(OR³)_(w)(OR³)_(w) and M²(OR²)_(v−w)(R³)_(w) may be alsoreferred herein as activating compounds.

In this step either one or both types of activating compounds (viz.activating electron donor or metal alkoxides) may be used.

The advantage of the use of this activation step prior to contacting thesolid support with the halogen-containing titanium compound (processphase C) is that a higher yield of polyolefins is obtained per gram ofthe procatalyst. Moreover, the ethylene sensitivity of the catalystsystem in the copolymerisation of propylene and ethylene is alsoincreased because of this activation step. This activation step isdisclosed in detail in WO2007/134851 of the present applicant.

Examples of suitable activating electron donors that may be used in stepii) are known to the skilled person and described herein below, i.e.include carboxylic acids, carboxylic acid anhydrides, carboxylic acidesters, carboxylic acid halides, alcohols, ethers, ketones, amines,amides, nitriles, aldehydes, alkoxides, sulphonamides, thioethers,thioesters and other organic compounds containing one or more heteroatoms, such as nitrogen, oxygen, sulphur and/or phosphorus.

Preferably, an alcohol is used as the activating electron donor in stepii). More preferably, the alcohol is a linear or branched aliphatic oraromatic alcohol having 1-12 carbon atoms. Even more preferably, thealcohol is selected from methanol, ethanol, butanol, isobutanol,hexanol, xylenol and benzyl alcohol. Most preferably, the alcohol isethanol or methanol, preferably ethanol.

Suitable carboxylic acids as activating electron donor may be aliphaticor (partly) aromatic. Examples include formic acid, acetic acid,propionic acid, butyric acid, isobutanoic acid, acrylic acid,methacrylic acid, maleic acid, fumaric acid, tartaric acid,cyclohexanoic monocarboxylic acid, cis-1,2-cyclohexanoic dicarboxylicacid, phenylcarboxylic acid, toluenecarboxylic acid, naphthalenecarboxylic acid, phthalic acid, isophthalic acid, terephthalic acidand/or trimellitic acid.

Anhydrides of the aforementioned carboxylic acids can be mentioned asexamples of carboxylic acid anhydrides, such as for example acetic acidanhydride, butyric acid anhydride and methacrylic acid anhydride.

Suitable examples of esters of above-mentioned carboxylic acids areformates, for instance, butyl formate; acetates, for instance ethylacetate and butyl acetate; acrylates, for instance ethyl acrylate,methyl methacrylate and isobutyl methacrylate; benzoates, for instancemethylbenzoate and ethylbenzoate; methyl-p-toluate; ethyl-naphthate andphthalates, for instance monomethyl phthalate, dibutyl phthalate,diisobutyl phthalate, diallyl phthalate and/or diphenyl phthalate.

Examples of suitable carboxylic acid halides as activating electrondonors are the halides of the carboxylic acids mentioned above, forinstance acetyl chloride, acetyl bromide, propionyl chloride, butanoylchloride, butanoyl iodide, benzoyl bromide, p-toluyl chloride and/orphthaloyl dichloride.

Suitable alcohols are linear or branched aliphatic alcohols with 1-12C-atoms, or aromatic alcohols. Examples include methanol, ethanol,butanol, isobutanol, hexanol, xylenol and benzyl alcohol. The alcoholsmay be used alone or in combination. Preferably, the alcohol is ethanolor hexanol.

Examples of suitable ethers are diethers, such as for example2-ethyl-2-butyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane and/or9,9-bis(methoxymethyl)fluorene. Also, cyclic ethers like tetrahydrofuran(THF), or tri-ethers can be used.

Suitable examples of other organic compounds containing a heteroatom asactivating electron donor include 2,2,6,6-tetramethyl piperidine,2,6-dimethylpiperidine, pyridine, 2-methylpyridine, 4-methylpyridine,imidazole, benzonitrile, aniline, diethylamine, dibutylamine,dimethylacetamide, thiophenol, 2-methyl thiophene, isopropyl mercaptan,diethylthioether, diphenylthioether, tetrahydrofuran, dioxane,dimethylether, diethylether, anisole, acetone, triphenylphosphine,triphenylphosphite, diethylphosphate and/or diphenylphosphate.

Examples of suitable metal alkoxides for use in step ii) are metalalkoxides of formulas: M¹(OR²)_(v−w)(OR³)_(w) and M²(OR²)_(v−w)(R³)_(w)wherein M¹, M², R², R³, v, and w are as defined herein. R² and R³ canalso be aromatic hydrocarbon groups, optionally substituted with e.g.alkyl groups and can contain for example from 6 to 20 carbon atoms. TheR² and R³ preferably comprise 1-12 or 1-8 carbon atoms. In preferredembodiments R² and R³ are ethyl, propyl or butyl; more preferably allgroups are ethyl groups.

Preferably, M¹ in said activating compound is Ti or Si. Si-containingcompounds suitable as activating compounds are the same as listed abovefor step i).

The value of w is preferably 0, the activating compound being forexample a titanium tetraalkoxide containing 4-32 carbon atoms in totalfrom four alkoxy groups. The four alkoxide groups in the compound may bethe same or may differ independently. Preferably, at least one of thealkoxy groups in the compound is an ethoxy group. More preferably thecompound is a tetraalkoxide, such as titanium tetraethoxide.

In the preferred process to prepare the procatalyst, one activatingcompound can be used, but also a mixture of two or more compounds may beused.

A combination of a compound of M¹(OR²)_(v−w)(OR³)_(w) orM²(OR²)_(v−w)(R³)_(w) with an electron donor is preferred as activatingcompound to obtain a catalyst system that for example shows highactivity, and of which the ethylene sensitivity can be affected byselecting the internal donor; which is specifically advantageous inpreparing copolymers of for example propylene and ethylene.

Preferably, a Ti-based compound, for example titanium tetraethoxide, isused together with an alcohol, like ethanol or hexanol, or with an estercompound, like ethylacetate, ethylbenzoate or a phthalate ester, or withpyridine.

If two or more activating compounds are used in step ii) their order ofaddition is not critical, but may affect catalyst performance dependingon the compounds used. A skilled person may optimize their order ofaddition based on some experiments. The compounds of step ii) can beadded together or sequentially.

Preferably, an electron donor compound is first added to the compoundwith formula Mg(OR¹)_(x)X¹ _(2−x) where after a compound of formulaM¹(OR²)_(v−w)(OR³)_(w) or M²(OR²)_(v−w)(R³)_(w) as defined herein isadded. The activating compounds preferably are added slowly, forinstance during a period of 0.1-6, preferably during 0.5-4 hours, mostpreferably during 1-2.5 hours, each.

The first intermediate reaction product that is obtained in step i) canbe contacted—when more than one activating compound is used—in anysequence with the activating compounds. In one embodiment, an activatingelectron donor is first added to the first intermediate reaction productand then the compound M¹(OR²)_(v−w)(OR³)_(w) or M²(OR²)_(v−w)(R³)_(w) isadded; in this order no agglomeration of solid particles is observed.The compounds in step ii) are preferably added slowly, for instanceduring a period of 0.1-6, preferably during 0.5-4 hours, most preferablyduring 1-2.5 hours, each.

The molar ratio of the activating compound to Mg(OR¹)_(x)X¹ _(2−x) mayrange between wide limits and is, for instance, from 0.02 to 1.0.Preferably, the molar ratio is from 0.05 to 0.5, more preferably from0.06 to 0.4, or even from 0.07 to 0.2.

The temperature in step ii) can be in the range from −20° C. to 70° C.,preferably from −10° C. to 50° C., more preferably in the range from −5°C. to 40° C., and most preferably in the range from 0° C. to 30° C.

Preferably, at least one of the reaction components is dosed in time,for instance during 0.1 to 6, preferably during 0.5 to 4 hours, moreparticularly during 1-2.5 hours.

The reaction time after the activating compounds have been added ispreferably from 0 to 3 hours.

The mixing speed during the reaction depends on the type of reactor usedand the scale of the reactor used. The mixing speed can be determined bya person skilled in the art and should be sufficient to agitate thereactants.

The inert dispersant used in step ii) is preferably a hydrocarbonsolvent. The dispersant may be for example an aliphatic or aromatichydrocarbon with 1-20 carbon atoms. Preferably, the dispersant is analiphatic hydrocarbon, more preferably pentane, iso-pentane, hexane orheptane, heptane being most preferred.

Starting from a solid Mg-containing product of controlled morphologyobtained in step i), said morphology is not negatively affected duringtreatment with the activating compound during step ii). The solid secondintermediate reaction product obtained in step ii) is considered to bean adduct of the Mg-containing compound and the at least one activatingcompound as defined in step ii), and is still of controlled morphology.

The obtained second intermediate reaction product after step ii) may bea solid and may be further washed, preferably with the solvent also usedas inert dispersant; and then stored and further used as a suspension insaid inert solvent. Alternatively, the product may be dried, preferablypartly dried, preferably slowly and under mild conditions; e.g. atambient temperature and pressure.

Phase C: Contacting said Solid Support with the Catalytic Species andone or more Internal Donors or an Activator.

Phase C: contacting the solid support with a catalytic species. Thisstep can take different forms, such as i) contacting said solid supportwith the catalytic species and one or more internal donors to obtainsaid procatalyst; ii) contacting said solid support with a catalyticspecies and one or more internal donors to obtain an intermediateproduct; iii) contacting said solid support with a catalytic species andan activator to obtain an intermediate product.

Phase C may comprise several stages. During each of these consecutivestages the solid support is contacted with said catalytic species. Inother words, the addition or reaction of said catalytic species may berepeated one or more times.

For example, during stage I of phase C said solid support (firstintermediate) or the activated solid support (second intermediate) isfirst contacted with said catalytic species and optionally subsequentlywith an internal donor. When a second stage is present, during stage IIthe intermediate product obtained from stage I will be contacted withadditional catalytic species which may the same or different than thecatalytic species added during the first stage and optionally aninternal donor. In case three stages are present, stage III ispreferably a repetition of stage II or may comprise the contacting ofthe product obtained from stage II with both a catalytic species (whichmay be the same or different as above) and an internal donor. In otherwords, an internal donor may be added during each of these stages orduring two or more of these stages. When an internal donor is addedduring more than one stage it may be the same or a different internaldonor. An internal donor according to Formula A is added during at leastone of the stages of Phase C.

An activator according to the present invention—if used—may be addedeither during stage I or stage II or stage III. An activator may also beadded during more than one stage.

Preferably, the process of contacting said solid support with thecatalytic species and an internal donor comprises the following stepiii).

Step iii) Reacting the Solid Support with a Transition Metal Halide

Step iii) reacting the solid support with a transition metal halide(e.g. titanium, chromium, hafnium, zirconium, vanadium) but preferablytitanium halide. In the discussion below only the process for atitanium-base Ziegler-Natta procatalyst is disclosed, however, theapplication is also applicable to other types of Ziegler-Nattaprocatalysts.

Step iii): contacting the first or second intermediate reaction product,obtained respectively in step i) or ii), with a halogen-containingTi-compound and optionally an internal electron donor or activator toobtain a third intermediate product.

Step iii) can be carried out after step i) on the first intermediateproduct or after step ii) on the second intermediate product.

The molar ratio in step iii) of the transition metal to the magnesiumpreferably is from 10 to 100, most preferably, from 10 to 50.

Preferably, an internal electron donor is also present during step iii).Also mixtures of internal electron donors can be used. Examples ofinternal electron donors are disclosed below.

The molar ratio of the internal electron donor relative to the magnesiummay vary between wide limits, for instance from 0.01 to 0.75.Preferably, this molar ratio is from 0.02 to 0.4; more preferably from0.03 to 0.2; and most preferably from 0.04 to 0.08.

During contacting the second intermediate product and thehalogen-containing titanium compound, an inert dispersant is preferablyused. The dispersant preferably is chosen such that virtually all sideproducts formed are dissolved in the dispersant. Suitable dispersantsinclude for example aliphatic and aromatic hydrocarbons and halogenatedaromatic solvents with for instance 4-20 carbon atoms. Examples includetoluene, xylene, benzene, heptane, o-chlorotoluene and chlorobenzene.

The reaction temperature during step iii) is preferably from 0° C. to150° C., more preferably from 50° C. to 150° C., and more preferablyfrom 100° C. to 140° C. Most preferably, the reaction temperature isfrom 110° C. to 125° C.

The reaction time during step iii) is preferably from 10 minutes to 10hours. In case several stages are present, each stage can have areaction time from 10 minutes to 10 hours. The reaction time can bedetermined by a person skilled in the art based on the reactor and theprocatalyst.

The mixing speed during the reaction depends on the type of reactor usedand the scale of the reactor used. The mixing speed can be determined bya person skilled in the art and should be sufficient to agitate thereactants.

The obtained reaction product may be washed, usually with an inertaliphatic or aromatic hydrocarbon or halogenated aromatic compound, toobtain the procatalyst of the invention. If desired the reaction andsubsequent purification steps may be repeated one or more times. A finalwashing is preferably performed with an aliphatic hydrocarbon to resultin a suspended or at least partly dried procatalyst, as described abovefor the other steps.

Optionally an activator is present during step iii) of Phase C insteadof an internal donor, this is explained in more detail below in thesection of activators.

The molar ratio of the activator relative to the magnesium may varybetween wide limits, for instance from 0.02 to 0.5. Preferably, thismolar ratio is from 0.05 to 0.4; more preferably from 0.1 to 0.3; andmost preferably from 0.1 to 0.2.

Phase D: Modifying said Intermediate Product with a Metal-BasedModifier.

This phase D is optional in the present invention. In a preferredprocess for modifying the supported catalyst, this phase consists of thefollowing steps: Step iv) modifying the third intermediate product witha metal-modifier to yield a modified intermediate product; Step v)contacting said modified intermediate product with a titanium halide andoptionally on or more internal donors to obtain the present procatalyst.

The order of addition, viz. the order of first step iv) and subsequentlystep v) is considered to be very important to the formation of thecorrect clusters of Group 13- or transition metal and titanium formingthe modified and more active catalytic center.

Each of these steps is disclosed in more detail below. It should benoted that the steps iii), iv) and v) (viz. phases C and D) arepreferably carried out in the same reactor, viz. in the same reactionmixture, directly following each other.

Preferably step iv) is carried out directly after step iii) in the samereactor. Preferably, step v) is carried out directly after step iv) inthe same reactor.

Step iv): Group 13- or Transition Metal Modification

The modification with Group 13- or transition metal, preferablyaluminium, ensures the presence of Group 13- or transition metal in theprocatalyst, in addition to magnesium (from the solid support) andtitanium (from the titanation treatment).

Without wishing to be bound by any particular theory, the presentinventors believe that one possible explanation is that the presence ofGroup 13- or transition metal increases the reactivity of the activesite and hence increases the yield of polymer.

Step iv) comprises modifying the third intermediate product obtained instep iii) with a modifier having the formula MX₃, wherein M is a metalselected from the Group 13 metals and transition metals of the IUPACperiodic table of elements, and wherein X is a halide to yield amodified intermediate product.

Step iv) is preferably carried out directly after step iii), morepreferably in the same reactor and preferably in the same reactionmixture. In an embodiment, a mixture of aluminum trichloride and asolvent, e.g. chlorobenzene, is added to the reactor after step iii) hasbeen carried out. After the reaction has completed a solid is allowed tosettle which can either be obtained by decanting or filtration andoptionally purified or a suspension of which in the solvent can be usedfor the following step, viz. step v).

The metal modifier is preferably selected from the group of aluminiummodifiers (e.g. aluminium halides), boron modifiers (e.g. boronhalides), gallium modifiers (e.g. gallium halides), zinc modifiers (e.g.zinc halides), copper modifiers (e.g. copper halides), thalliummodifiers (e.g. thallium halides), indium modifiers (e.g. indiumhalides), vanadium modifiers (e.g. vanadium halides), chromium modifiers(e.g. chromium halides), iron modifiers (e.g. iron halides).

Examples of suitable modifiers are aluminum trichloride, aluminumtribromide, aluminum triiodide, aluminum trifluoride, boron trichloride,boron tribromide boron triiodide, boron trifluoride, galliumtrichloride, gallium tribromide, gallium triiodide, gallium trifluoride,zinc dichloride, zinc dibromide, zinc diiodide, zinc difluoride, copperdichloride, copper dibromide, copper diiodide, copper difluoride, copperchloride, copper bromide, copper iodide, copper fluoride, thalliumtrichloride, thallium tribromide, thallium triiodide, thalliumtrifluoride, thallium chloride, thallium bromide, thallium iodide,thallium fluoride, Indium trichloride, indium tribromide, indiumtriiodide, indium trifluoride, vanadium trichloride, vanadiumtribromide, vanadium triiodide, vanadium trifluoride, chromiumtrichloride, chromium dichloride, chromium tribromide, chromiumdibromide, iron dichloride, iron trichloride, iron tribromide, irondichloride, iron triiodide, iron diiodide, iron trifluoride, irondifluoride.

The amount of metal halide added during step iv) may vary according tothe desired amount of metal present in the procatalyst. It may forexample range from 0.01 to 5 wt. % based on the total weight of thesupport, preferably from 0.1 to 0.5 wt. % was carried out directly afterstep iii) in the same reactor.

The metal halide is preferably mixed with a solvent prior to theaddition to the reaction mixture. The solvent for this step may beselected from for example aliphatic and aromatic hydrocarbons andhalogenated aromatic solvents with for instance 4-20 carbon atoms.Examples include toluene, xylene, benzene, decane, o-chlorotoluene andchlorobenzene. The solvent may also be a mixture or two or more thereof.

The duration of the modification step may vary from 1 minute to 120minutes, preferably from 40 to 80 minutes, more preferably from 50 to 70minutes. This time is dependent on the concentration of the modifier,the temperature, the type of solvent used etc.

The modification step is preferably carried out at elevated temperatures(e.g. from 50 to 120° C., preferably from 90 to 110° C.).

The modification step may be carried out while stirring. The mixingspeed during the reaction depends on the type of reactor used and thescale of the reactor used. The mixing speed can be determined by aperson skilled in the art. As a non-limiting example, mixing may becarried at a stirring speed from 100 to 400 rpm, preferably from 150 to300 rpm, more preferably about 200 rpm).

The wt/vol ratio for the metal halide and the solvent in step iv) isfrom 0.01 gram −0.1 gram : 5.0−100 ml.

The modified intermediate product is present in a solvent. It can bekept in that solvent after which the following step v) is directlycarried out. However, it can also be isolated and/or purified. The solidcan be allowed to settle by stopping the stirring. The supernatant canthen be removed by decanting. Otherwise, filtration of the suspension isalso possible. The solid product may be washed once or several timeswith the same solvent used during the reaction or another solventselected from the same group described above. The solid may beresuspended or may be dried or partially dried for storage.

Subsequent to this step, step v) is carried out to produce theprocatalyst according to the present invention.

Step v): Additional Treatment of Intermediate Product.

This step is very similar to step iii). It contains the additionaltreatment of the modified intermediate product.

Step v) contacting said modified intermediate product obtained in stepiv) with a halogen-containing titanium compound to obtain theprocatalyst according to the present invention. When an activator isused during step iii) an internal donor is used during this step.

Step v) is preferably carried out directly after step iv), morepreferably in the same reactor and preferably in the same reactionmixture.

In an embodiment, at the end of step iv) or at the beginning of step v)the supernatant was removed from the solid modified intermediate productobtained in step iv) by filtration or by decanting. To the remainingsolid, a mixture of titanium halide (e.g. tetrachloride) and a solvent(e.g. chlorobenzene) can be added. The reaction mixture is subsequentlykept at an elevated temperature (e.g. from 100 to 130° C., such as 115°C.) for a certain period of time (e.g. from 10 to 120 minutes, such asfrom 20 to 60 minutes, e.g. 30 minutes). After this, a solid substancewas allowed to settle by stopping the stirring.

The molar ratio of the transition metal to the magnesium preferably isfrom 10 to 100, most preferably, from 10 to 50.

Optionally, additional internal electron donor may also present duringthis step. Also mixtures of internal electron donors can be used. Themolar ratio of the internal electron donor relative to the magnesium mayvary between wide limits, for instance from 0.02 to 0.75. Preferably,this molar ratio is from 0.05 to 0.4; more preferably from 0.1 to 0.4;and most preferably from 0.1 to 0.3.

The solvent for this step may be selected from for example aliphatic andaromatic hydrocarbons and halogenated aromatic solvents with forinstance 4-20 carbon atoms. The solvent may also be a mixture or two ormore thereof.

According to a preferred embodiment of the present invention this stepv) is repeated, in other words, the supernatant is removed as describedabove and a mixture of titanium halide (e.g. tetrachloride) and asolvent (e.g. chlorobenzene) is added. The reaction is continued atelevated temperatures during a certain time which can be same ordifferent from the first time step v) is carried out.

The step may be carried out while stirring. The mixing speed during thereaction depends on the type of reactor used and the scale of thereactor used. The mixing speed can be determined by a person skilled inthe art. This can be the same as discussed above for step iii).

Thus, step v) can be considered to consist of at least two sub steps inthis embodiment, being:

v-a) contacting said modified intermediate product obtained in step iv)with titanium tetrachloride—optionally using an internal donor—to obtaina partially titanated procatalyst;

v-b) contacting said partially titanated procatalyst obtained in stepv-a) with titanium tetrachloride to obtain the procatalyst.

Additional sub steps can be present to increase the number of titanationsteps to four or higher.

The solid substance (procatalyst) obtained was washed several times witha solvent (e.g. heptane), preferably at elevated temperature, e.g. from40 to 100° C. depending on the boiling point of the solvent used,preferably from 50 to 70° C. After this, the procatalyst, suspended insolvent, was obtained. The solvent can be removed by filtration ordecantation. The procatalyst can be used as such wetted by the solventor suspended in solvent or it can be first dried, preferably partlydried, for storage. Drying can e.g. be carried out by low pressurenitrogen flow for several hours.

Thus in this embodiment, the total titanation treatment comprises threephases of addition of titanium halide. Wherein the first phase ofaddition is separated from the second and third phases of addition bythe modification with metal halide.

It could be said that the difference between the prior art and thepresent invention is that the titanation step (viz. the step ofcontacting with a titanium halide) according to the present invention issplit into two parts and a Group 13- or transition metal modificationstep is introduced between the two parts or stages of the titanation.Preferably, the first part of the titanation comprises one singletitanation step and the second part of the titanation comprises twosubsequent titanation steps. When this modification is carried outbefore the titanation step the increase in activity was higher asobserved by the inventors. When this modification is carried out afterthe titanation step the increase in activity was less as observed by thepresent inventors.

In short, an embodiment of the present invention comprises the followingsteps: i) preparation of first intermediate reaction product; ii)activation of solid support to yield second intermediate reactionproduct; iii) first titanation or Stage I to yield third intermediatereaction product; iv) modification to yield modified intermediateproduct; v) second titanation or Stage II/III to yield the procatalyst.

The procatalyst may have a titanium, hafnium, zirconium, chromium orvanadium (preferably titanium) content of from about 0.1 wt % to about6.0 wt %, based on the total solids weight, or from about 1.0 wt % toabout 4.5 wt %, or from about 1.5 wt % to about 3.5 wt %.

The weight ratio of titanium, hafnium, zirconium, chromium or vanadium(preferably titanium) to magnesium in the solid procatalyst may be fromabout 1:3 to about 1:160, or from about 1:4 to about 1:50, or from about1:6 to 1:30. Weight percentage is based on the total weight of theprocatalyst.

This process according to the present invention results in a procatalysthaving a high hydrogen sensitivity which allow obtaining polyolefins,preferably polypropylene having a medium molecular weight distribution.

The transition metal-containing solid catalyst compound according to thepresent invention comprises a transition metal halide (e.g. titaniumhalide, chromium halide, hafnium halide, zirconium halide, vanadiumhalide) supported on a metal or metalloid compound (e.g. a magnesiumcompound or a silica compound).

Preferably, a magnesium-based or magnesium-containing support is used inthe present invention. Such a support is prepared frommagnesium-containing support-precursors, such as magnesium halides,magnesium alkyls and magnesium aryls, and also magnesium alkoxy andmagnesium aryloxy compounds.

The support may be activated using activation compounds as described inmore detail above under Phase B.

The intermediate product may further be activated during Phase C asdiscussed above for the process. This activation increases the yield ofthe resulting procatalyst in olefin polymerisation.

Several activators can be used, such as benzamide, alkylbenzoates, andmonoesters. Each of these will be discussed below.

A benzamide activator has a structure according to formula X:

R⁷⁰ and R⁷¹ are each independently selected from hydrogen or an alkyl.Preferably, said alkyl has from 1 to 6 carbon atoms, more preferablyfrom 1 to 3 carbon atoms. More preferably, R⁷⁰ and R⁷¹ are eachindependently selected from hydrogen or methyl.

R⁷², R⁷³, R⁷⁴, R⁷⁵, R⁷⁶ are each independently selected from hydrogen, aheteroatom (preferably a halide), or a hydrocarbyl group, selected fromalkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, andone or more combinations thereof. Said hydrocarbyl group may be linear,branched or cyclic. Said hydrocarbyl group may be substituted orunsubstituted. Said hydrocarbyl group may contain one or moreheteroatoms. Preferably, said hydrocarbyl group has from 1 to 10 carbonatoms, more preferably from 1 to 8 carbon atoms, even more preferablyfrom 1 to 6 carbon atoms.

Suitable non-limiting examples of “benzamides” include benzamide (R⁷⁰and R⁷¹ are both hydrogen and each of R⁷², R⁷³, R⁷⁴, R⁷⁵, R⁷⁶ arehydrogen) also denoted as BA-2H or methylbenzamide (R⁷⁰ is hydrogen; R⁷¹is methyl and each of R⁷², R⁷³, R⁷⁴, R⁷⁵, R⁷⁶ are hydrogen) also denotedas BA-HMe or dimethylbenzamide (R⁷⁰ and R⁷¹ are methyl and each of R⁷²,R⁷³, R⁷⁴, R⁷⁵, R⁷⁶ are hydrogen) also denoted as BA-2Me. Other examplesinclude monoethylbenzamide, diethylbenzamide, methylethylbenzamide,2-(trifluor-methyl)benzamide, N,N-dimethyl-2-(trifluormethyl)benzamide,3-(trifluormethyl)-benzamide, N,N-dimethyl-3-(trifluormethyl)benzamide,2,4-dihydroxy-N-(2-hydroxyethyl)-benzamide,N-(1H-benzotriazol-1-ylmethyl)benzamide, 1-(4-ethylbenzoyl)piperazine,1-benzoylpiperidine.

Without wishing to be bound by a particular theory the present inventorsbelieve that the fact that the most effective activation is obtainedwhen the benzamide activator is added during stage I has the followingreason. It is believed that the benzamide activator will bind thecatalytic species and is later on substituted by the internal donor whenthe internal donor is added.

Alkylbenzoates may be used as activators. The activator may hence beselected from the group alkylbenzoates having an alkylgroup having from1 to 10, preferably from 1 to 6 carbon atoms. Examples of suitable alkylbenzoates are methylbenzoate, ethylbenzoate according to Formula II,n-propylbenzoate, iso-propylbenzoate, n-butylbenzoate, 2-butylbenzoate,t-butylbenzoate.

More preferably, the activator is ethylbenzoate.

Mono-esters may be used as activators. The monoester according to thepresent invention can be any ester of a monocarboxylic acid known in theart. The structures according to Formula V are also mono-esters but arenot explained in this section, see the section on Formula V. Themonoester can have the formula XXIII:R⁹⁴—CO—OR⁹⁵  Formula XXIII

R⁹⁴ and R⁹⁵ are each independently selected from a hydrogen or ahydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl,alkoxycarbonyl or alkylaryl groups, and one or more combinationsthereof. Said hydrocarbyl group may be linear, branched or cyclic. Saidhydrocarbyl group may be substituted or unsubstituted. Said hydrocarbylgroup may contain one or more heteroatoms. Preferably, said hydrocarbylgroup has from 1 to 10 carbon atoms, more preferably from 1 to 8 carbonatoms, even more preferably from 1 to 6 carbon atoms. When R⁹⁴ is anaryl, this structure is similar to Formula V. Examples of aromaticmono-esters are discussed with reference to formula V.

Preferably said mono-ester is an aliphatic monoester. Suitable examplesof mono-esters include formates, for instance, butyl formate; acetates,for instance ethyl acetate, amyl acetate and butyl acetate; acrylates,for instance ethyl acrylate, methyl methacrylate and isobutylmethacrylate. More preferably, the aliphatic monoester is an acetate.Most preferably, the aliphatic monoester is ethyl acetate.

In an embodiment, the monoester used in step iii) is an ester of analiphatic monocarboxylic acid having from 1 to 10 carbon atoms. WhereinR⁹⁴ is an aliphatic hydrocarbyl group.

The molar ratio between the monoester in step iii) and Mg may range from0.05 to 0.5, preferably from 0.1 to 0.4, and most preferably from 0.15to 0.25.

The monoester is not used as a stereospecificity agent, like usualinternal donors are known to be in the prior art. The monoester is usedas an activator.

Without to be bound by any theory, the inventors believe that themonoester used in the process according to the present inventionparticipates at the formation of the magnesium halogen (e.g. MgCl₂)crystallites during the interaction of Mg-containing support withtitanium halogen (e.g. TiCl₄). The monoester may form intermediatecomplexes with Ti and Mg halogen compounds (for instance, TiCl₄,TiCl₃(OR), MgCl₂, MgCl(OEt), etc.), help to the removal of titaniumproducts from solid particles to mother liquor and affect the activityof final catalyst. Therefore, the monoester according to the presentinvention can also be referred to as an activator.

The catalyst system according to the present invention includes aco-catalyst. As used herein, a “co-catalyst” is a term well-known in theart in the field of Ziegler-Natta catalysts and is recognized to be asubstance capable of converting the procatalyst to an activepolymerization catalyst. Generally, the co-catalyst is an organometalliccompound containing a metal from group 1, 2, 12 or 13 of the PeriodicSystem of the Elements (Handbook of Chemistry and Physics, 70th Edition,CRC Press, 1989-1990).

The co-catalyst may include any compounds known in the art to be used as“co-catalysts”, such as hydrides, alkyls, or aryls of aluminum, lithium,zinc, tin, cadmium, beryllium, magnesium, and combinations thereof. Theco-catalyst may be a hydrocarbyl aluminum co-catalyst represented by theFischer projection of the formula R²⁰ ₃Al.

R²⁰ is independently selected from a hydrogen or a hydrocarbyl, selectedfrom alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups,and one or more combinations thereof. Said hydrocarbyl group may belinear, branched or cyclic. Said hydrocarbyl group may be substituted orunsubstituted. Said hydrocarbyl group may contain one or moreheteroatoms. Preferably, said hydrocarbyl group has from 1 to 20 carbonatoms, more preferably from 1 to 12 carbon atoms, even more preferablyfrom 1 to 6 carbon atoms. On the proviso that at least one R²⁰ is ahydrocarbyl group. Optionally, two or three R²⁰ groups are joined in acyclic radical forming a heterocyclic structure.

Non-limiting examples of suitable R²⁰ groups are: methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl,2-methylpentyl, heptyl, octyl, isooctyl, 2-ethylhexyl,5,5-dimethylhexyl, nonyl, decyl, isodecyl, undecyl, dodecyl, phenyl,phenethyl, methoxyphenyl, benzyl, tolyl, xylyl, naphthyl, methylnapthyl,cyclohexyl, cycloheptyl, and cyclooctyl.

Suitable examples of the hydrocarbyl aluminum compounds as co-catalystinclude triisobutylaluminum, trihexylaluminum, di-isobutylaluminumhydride, dihexylaluminum hydride, isobutylaluminum dihydride,hexylaluminum dihydride, diisobutylhexylaluminum, isobutyldihexylaluminum, trimethylaluminum, triethylaluminum, tripropylaluminum,triisopropylaluminum, tri-n-butylaluminum, trioctylaluminum,tridecylaluminum, tridodecylaluminum, tribenzylaluminum,triphenylaluminum, trinaphthylaluminum, and tritolylaluminum. In anembodiment, the cocatalyst is selected from triethylaluminum,triisobutylaluminum, trihexylaluminum, di-isobutylaluminum hydride anddihexylaluminum hydride. More preferably, trimethylaluminium,triethylaluminium, triisobutylaluminium, and/or trioctylaluminium. Mostpreferably, triethylaluminium (abbreviated as TEAL).

Preferably, the co-catalyst is triethylaluminum. The molar ratio ofaluminum to titanium may be from about 5:1 to about 500:1 or from about10:1 to about 200:1 or from about 15:1 to about 150:1 or from about 20:1to about 100:1. The molar ratio of aluminum to titanium is preferablyabout 45:1.

One of the functions of an external donor compound is to affect thestereoselectivity of the catalyst system in polymerization of olefinshaving three or more carbon atoms. Therefore it may be also referred toas a selectivity control agent.

Examples of external donors suitable for use in the present inventionare benzoic acid esters, 1,3-diethers, alkylamino-alkoxysilanes,alkyl-alkoxysilane, imidosilanes, and alkylimidosilanes.

The aluminium/external donor molar ratio in the polymerization catalystsystem preferably is from 0.1 to 200; more preferably from 1 to 100.

Mixtures of external donors may be present and may include from about0.1 mol % to about 99.9% mol % of a first external donor and from about99.9 mol % to about 0.1 mol % of either a second or the additionalalkoxysilane external donor disclosed below.

When a silane external donor is used, the Si/Ti molar ratio in thecatalyst system can range from 0.1 to 40, preferably from 0.1 to 20,even more preferably from 1 to 20 and most preferably from 2 to 10.

A benzoic acid ester can be used as internal donor. It is amonocarboxylic acid ester as shown in Formula V.

R³⁰ is selected from a hydrocarbyl group independently selected fromalkyl, alkenyl, aryl, aralkyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be linear, branched orcyclic. Said hydrocarbyl group may be substituted or unsubstituted. Saidhydrocarbyl group may contain one or more heteroatoms. Preferably, saidhydrocarbyl group has from 1 to 10 carbon atoms, more preferably from 1to 8 carbon atoms, even more preferably from 1 to 6 carbon atoms.Suitable examples of hydrocarbyl groups include alkyl-, cycloalkyl-,alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl,alkylaryl, and alkynyl-groups.

R³¹, R³², R³³, R³⁴, R³⁵ are each independently selected from hydrogen, aheteroatom (preferably a halide), or a hydrocarbyl group, selected frome.g. alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups,and one or more combinations thereof. Said hydrocarbyl group may belinear, branched or cyclic. Said hydrocarbyl group may be substituted orunsubstituted. Said hydrocarbyl group may contain one or moreheteroatoms. Preferably, said hydrocarbyl group has from 1 to 10 carbonatoms, more preferably from 1 to 8 carbon atoms, even more preferablyfrom 1 to 6 carbon atoms.

Suitable non-limiting examples of “benzoic acid esters” include an alkylp-alkoxybenzoate (such as ethyl p-methoxybenzoate, methylp-ethoxybenzoate, ethyl p-ethoxybenzoate), an alkyl benzoate (such asethyl benzoate, methyl benzoate), an alkyl p-halobenzoate (ethylp-chlorobenzoate, ethyl p-bromobenzoate), and benzoic anhydride. Thebenzoic acid ester is preferably selected from ethyl benzoate, benzoylchloride, ethyl p-bromobenzoate, n-propyl benzoate and benzoicanhydride. The benzoic acid ester is more preferably ethyl benzoate.

In an embodiment the external donor used is ethyl benzoate. In anotherembodiment, the external donor used is ethyl p-ethoxybenzoate.

As used herein a “di-ether” may be a 1,3-di(hydrocarboxy)propanecompound, optionally substituted on the 2-position represented by theFischer projection of the Formula VII,

R⁵¹ and R⁵² are each independently selected from a hydrogen or ahydrocarbyl group selected from alkyl, alkenyl, aryl, aralkyl,alkoxycarbonyl or alkylaryl groups, and one or more combinationsthereof. Said hydrocarbyl group may be linear, branched or cyclic. Saidhydrocarbyl group may be substituted or unsubstituted. Said hydrocarbylgroup may contain one or more heteroatoms. Preferably, said hydrocarbylgroup has from 1 to 10 carbon atoms, more preferably from 1 to 8 carbonatoms, even more preferably from 1 to 6 carbon atoms. Suitable examplesof hydrocarbyl groups include alkyl-, cycloalkyl-, alkenyl-,alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl, alkylaryl,and alkynyl-groups.

R⁵³ and R⁵⁴ are each independently selected from hydrogen, a halide or ahydrocarbyl group, selected from alkyl, alkenyl, aryl, aralkyl,alkoxycarbonyl or alkylaryl groups, and one or more combinationsthereof. Said hydrocarbyl group may be linear, branched or cyclic. Saidhydrocarbyl group may be substituted or unsubstituted. Said hydrocarbylgroup may contain one or more heteroatoms. Preferably, said hydrocarbylgroup has from 1 to 10 carbon atoms, more preferably from 1 to 8 carbonatoms, even more preferably from 1 to 6 carbon atoms.

Suitable examples of dialkyl diether compounds include1,3-dimethoxypropane, 1,3-diethoxypropane, 1,3-dibutoxypropane,1-methoxy-3-ethoxypropane, 1-methoxy-3-butoxypropane,1-methoxy-3-cyclohexoxypropane, 2,2-dimethyl-1,3-dimethoxypropane,2,2-diethyl-1,3-dimethoxypropane, 2,2-di-n-butyl-1,3-dimethoxypropane,2,2-diiso-butyl-1,3-dimethoxypropane,2-ethyl-2-n-butyl-1,3-dimethoxypropane,2-n-propyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dimethyl-1,3-diethoxypropane,2-n-propyl-2-cyclohexyl-1,3-diethoxypropane,2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-isopropyl-1,3-dimethoxypropane,2-n-butyl-1,3-dimethoxypropane, 2-sec-butyl-1,3-dimethoxypropane,2-cyclohexyl-1,3-dimethoxypropane, 2-phenyl-1,3-diethoxypropane,2-cumyl-1,3-diethoxypropane, 2-(2-phenyllethyl)-1,3-dimethoxypropane,2-(2-cyclohexylethyl)-1 ,3-dimethoxypropane,2-(p-chlorophenyl)-1,3-dimethoxypropane,2-(diphenylmethyl)-1,3-dimethoxypropane,2-(1-naphthyl)-1,3-dimethoxypropane,2-(fluorophenyl)-1,3-dimethoxypropane,2-(1-decahydronaphthyl)-1,3-dimethoxypropane,2-(p-t-butylphenyI)-1,3-dimethoxypropane,2,2-dicyclohexyl-1,3-dimethoxypropane,2,2-di-npropyl-1,3-dimethoxypropane,2-methyl-2-n-propyl-1,3-dimethoxypropane,2-methyl-2-benzyl-1,3-dimethoxypropane,2-methyl-2-ethyl-1,3-dimethoxypropane,2-methyl-2-phenyl-1,3-dimethoxypropane,2-methyl-2-cyclohexyl-1,3-dimethoxypropane,2,2-bis(pchlorophenyI)-1,3-dimethoxypropane,2,2-bis(2-cyclohexylethyl)-1,3-dimethoxypropane, 2-methyl-2-isobutyl-1,3-dimethoxypropane, 2-methyl-2-(2-ethylhexyl)-1,3-dimethoxypropane, 2-methyl-2-isopropyl-1,3-dimethoxypropane,2,2-diphenyl-1,3-dimethoxypropane, 2,2-dibenzyl-1,3-dimethoxypropane,2,2-bis(cyclohexylmethyl)-1,3-dimethoxypropane, 2,2-diisobutyl-1,3-diethoxypropane, 2,2-diisobuty 1-1,3-di -n-butoxypropane,2-iso butyl-2-isopropyl-1,3-dimethoxypropane,2,2-di-sec-butyl-1,3-dimethoxypropane,2,2-di-t-butyl-1,3-dimethoxypropane,2,2-dineopentyl-1,3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane,2-phenyl-2-benzyl-1,3-dimethoxypropane,2-cyclohexyl-2-cyclohexylmethyl-1,3-dimethoxypropane, 2-isopropyl-2-(3,7-dimethyloctyl) 1,3-dimethoxypropane,2,2-diisopropyl-1,3-dimethoxypropane,2-isopropyl-2-cyclohexylmethyl-1,3-dimethoxypropane,2,2-diisopentyl-1,3-dimethoxypropane,2-isopropyl-2-cyclohexyl-1,3-dimethoxypropane,2-isopropyl-2-cyclopentyl-1,3-dimethoxypropane,2,2-dicylopentyl-1,3-dimethoxypropane,2-n-heptyl-2-n-pentyl-1,3-dimethoxypropane,9,9-bis(methoxymethyl)fluorene,1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane,3,3-bis(methoxymethyl)-2,5-dimethylhexane, or any combination of theforegoing. In an embodiment, the internal electron donor is1,3-dicyclohexyl-2,2-bis(methoxymethyl)propane, 3,3-bis(methoxymethyl)-2,5-dimethylhexane,2,2-dicyclopentyl-1,3-dimethoxypropane and combinations thereof.

Examples of preferred ethers are diethyl ether, such as2-ethyl-2-butyl-1, 3-dimethoxypropane,2-isopropyl-2-isopentyl-1,3-dimethoxypropane and 9,9-bis (methoxymethyl)fluorene:

Documents EP1538167 and EP1783145 disclose a Ziegler-Natta catalyst typecomprising an organo-silicon compound as external donor that isrepresented by the Fischer projection of formulaSi(OR^(c))₃(NR^(d)R^(e)), wherein R^(c) is a hydrocarbon group having 1to 6 carbon atoms, R^(d) is a hydrocarbon group having 1 to 12 carbonatoms or hydrogen atom, and Re is a hydrocarbon group having 1 to 12carbon atoms used as an external electron donor.

An other example of a suitable external donor according to the presentinvention is a compound according to Formula III:(R⁹⁰)₂N-A-Si(OR⁹¹)₃

The R⁹⁰ and R⁹¹ groups are each independently an alkyl having from 1 to10 carbon atoms. Said alkyl group may be linear, branched or cyclic.Said alkyl group may be substituted or unsubstituted. Preferably, saidhydrocarbyl group has from 1 to 8 carbon atoms, even more preferablyfrom 1 to 6 carbon atoms, even more preferably from 2 to 4 carbon atoms.Preferably, each R⁹⁰ is ethyl. Preferably, each R⁹¹ is ethyl. A iseither a direct bond between nitrogen and silicon or a spacer selectedfrom an alkyl having 1-10 carbon atoms, preferably a direct bond.

An example of such an external donor is diethyl-amino-triethoxysilane(DEATES) wherein A is a direct bond, each R⁹° is ethyl and each R⁹¹ isethyl.

Alkyl-alkoxysilanes according to Formula IV may be used:(R⁹²)Si(OR⁹²′)₃  Formula IV

The R⁹² and R⁹²′ groups are each independently an alkyl having from 1 to10 carbon atoms. Said alkyl group may be linear, branched or cyclic.Said alkyl group may be substituted or unsubstituted. Preferably, saidhydrocarbyl group has from 1 to 8 carbon atoms, even more preferablyfrom 1 to 6 carbon atoms, even more preferably from 2 to 4 carbon atoms.Preferably, all three R⁹²′ groups are the same. Preferably, R⁹²′ ismethyl or ethyl. Preferably, R⁹² is ethyl or propyl, more preferablyn-propyl.

Typical external donors known in the art (for instance as disclosed indocuments WO2006/056338A1, EP1 838741 B1, U.S. Pat. No. 6,395,670B1,EP398698A1, WO96/32426A) are organosilicon compounds having generalformula Si(OR^(a))_(4−n)R^(b) _(n), wherein n can be from 0 up to 2, andeach R^(a) and R^(b), independently, represents an alkyl or aryl group,optionally containing one or more hetero atoms for instance O, N, S orP, with, for instance, 1-20 carbon atoms; such as n-propyltrimethoxysilane (nPTMS), n-propyl triethoxysilane (nPEMS), diisobutyldimethoxysilane (DiBDMS), tert-butyl isopropyl dimethyxysilane(tBiPDMS), cyclohexyl methyldimethoxysilane (CHMDMS), dicyclopentyldimethoxysilane (DCPDMS) or di(iso-propyl) dimethoxysilane (DiPDMS).

Imidosilanes according to Formula I may be used as external donors.Si(L)_(n)(OR¹¹)_(4−n),   Formula I

wherein,

Si is a silicon atom with valency 4+;

O is an oxygen atom with valency 2- and O is bonded to Si via asilicon-oxygen bond;

n is 1, 2, 3 or 4;

R¹¹ is selected from the group consisting of linear, branched and cyclicalkyl having at most 20 carbon atoms and aromatic substituted andunsubstituted hydrocarbyl having 6 to 20 carbon atoms; two R¹¹ groupscan be connected and together may form a cyclic structure; and

L is a group represented by the Fischer projection of Formula I″

wherein,

L is bonded to the silicon atom via a nitrogen-silicon bond;

L has a single substituent on the nitrogen atom, where this singlesubstituent is an imine carbon atom; and

X and Y are each independently selected from the group consisting of:

a) a hydrogen atom;

b) a group comprising a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements, through which X and Yare each independently bonded to the imine carbon atom of Formula II,wherein the heteroatom is substituted with a group consisting of alinear, branched and cyclic alkyl having at most 20 carbon atoms,optionally containing a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements; and/or with an aromaticsubstituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms,optionally containing a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements;

c) a linear, branched and cyclic alkyl having at most 20 carbon atoms,optionally containing a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements; and

d) an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20carbon atoms, optionally containing a heteroatom selected from group 13,14, 15, 16 or 17 of the IUPAC.

R¹¹ is selected from the group consisting of linear, branched and cyclicalkyl having at most 20 carbon atoms.

Preferably, R¹¹ is a selected from the group consisting of linear,branched and cyclic alkyl having at most 20 carbon atoms, preferably 1to 10 carbon atoms or 3 to 10 carbon atoms, more preferably 1 to 6carbon atoms.

Suitable examples of R¹¹ include methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, tert-butyl, sec-butyl, iso-butyl, n-pentyl,iso-pentyl, cyclopentyl, n-hexyl and cyclohexyl. More preferably, R¹¹ isa linear alkyl having 1 to 10, even more preferably 1 to 6 carbon atoms.Most preferably, R¹¹ is methyl or ethyl.

R¹² is selected from the group consisting of a linear, branched andcyclic hydrocarbyl group independently selected from alkyl, alkenyl,aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be substituted orunsubstituted. Said hydrocarbyl group may contain one or moreheteroatoms. Preferably, said hydrocarbyl group has from 1 to 20 carbonatoms.

Suitable examples of R¹² include methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, tert-butyl, sec-butyl, iso-butyl, n-pentyl,iso-pentyl, cyclopentyl, n-hexyl, cyclohexyl, unsubstituted orsubstituted phenyl.

Specific examples are the following compounds:1,1,1-triethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene) silanamine (allR¹¹ groups are=ethyl and X and Y are both tert-butyl);1,1,1-trimethoxy-N-(2,2,4,4-tetramethylpentan-3-ylidene) silanamine (allR¹¹ groups are methyl, and X and Y are tert butyl),N,N,N′,N′-tetramethylguanidine triethoxysilane (all R11 groups areethyl, both X and Y are dimethylamino). Alkylimidosilanes according toFormula I′ may be used as external donors.Si(L)_(n)(OR¹¹)_(4−n−m)(R¹²)_(m)   Formula I′

wherein,

Si is a silicon atom with valency 4+;

O is an oxygen atom with valency 2- and O is bonded to Si via asilicon-oxygen bond;

n is 1, 2, 3 or 4;

m is 0,1 or 2

n+m≤4

R¹¹ is selected from the group consisting of linear, branched and cyclicalkyl having at most 20 carbon atoms and aromatic substituted andunsubstituted hydrocarbyl having 6 to 20 carbon atoms; and

R¹² is selected from the group consisting of linear, branched and cyclicalkyl having at most 20 carbon atoms and aromatic substituted andunsubstituted hydrocarbyl having 6 to 20 carbon atoms;

L is a group represented by the Fischer projection of Formula I″

wherein,

L is bonded to the silicon atom via a nitrogen-silicon bond;

L has a single substituent on the nitrogen atom, where this singlesubstituent is an imine carbon atom; and

X and Y are each independently selected from the group consisting of:

a) a hydrogen atom;

b) a group comprising a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements, through which X and Yare each independently bonded to the imine carbon atom of Formula II,wherein the heteroatom is substituted with a group consisting of alinear, branched and cyclic alkyl having at most 20 carbon atoms,optionally containing a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements; and/or with an aromaticsubstituted and unsubstituted hydrocarbyl having 6 to 20 carbon atoms,optionally containing a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements;

c) a linear, branched and cyclic alkyl having at most 20 carbon atoms,optionally containing a heteroatom selected from group 13, 14, 15, 16 or17 of the IUPAC Periodic Table of the Elements; and

d) an aromatic substituted and unsubstituted hydrocarbyl having 6 to 20carbon atoms, optionally containing a heteroatom selected from group 13,14, 15, 16 or 17 of the IUPAC Periodic Table of the Elements.

R¹¹ and R12 are as discussed above.

In a first specific example, the external donor may have a structurecorresponding to Formula I′ wherein n=1, m=2, X═Y=phenyl, both R¹²groups are methyl, and R¹¹ is butyl.

In a second specific example, the external donor may have a structurecorresponding to Formula I′ wherein n=4, m=0, X=methyl, and Y=ethyl.

In a third specific example, the external donor may have a structurecorresponding to Formula I′ wherein n=1, m=1, X=phenyl, Y═—CH₂—Si(CH₃)₃,and R¹²=R¹¹=methyl.

In a fourth specific example, the external donor may have a structurecorresponding to Formula I′ wherein n=1, m=1, X═—NH—C═NH(NH₂)—,Y═—NH—(CH₂)₃—Si(OCH₂CH₃)₃, and R¹²═—(CH₂)₃—NH_(2;) R¹¹=ethyl.

The additional compound(s) in the external donor according to theinvention may be one or more alkoxysilanes. The alkoxysilane compoundcan have any of the structures disclosed herein. The alkoxysilane isdescribed by Formula IXSiR⁷ _(r)(OR⁸)_(4−r)   (Formula IX)

R⁷ is independently a hydrocarbyl, selected from alkyl, alkenyl, aryl,aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof. Said hydrocarbyl group may be linear, branched orcyclic. Said hydrocarbyl group may be substituted or unsubstituted. Saidhydrocarbyl group may contain one or more heteroatoms. Preferably, saidhydrocarbyl group has from 1 to 20 carbon atoms, more preferably from 6to 12 carbon atoms, even more preferably from 3 to 12 carbon atoms. Forexample, R⁷ may be C6-12 aryl, alkyl or aralkyl, C3-12 cycloalkyl, C3-12branched alkyl, or C3-12 cyclic or acyclic amino group. The value for ris selected from 1 or 2.

For the formula SiNR⁷r(OR⁸)_(4−r)R⁷ may also be hydrogen.

R⁸ is independently selected from a hydrogen or a hydrocarbyl, selectedfrom alkyl, alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups,and one or more combinations thereof. Said hydrocarbyl group may belinear, branched or cyclic. Said hydrocarbyl group may be substituted orunsubstituted. Said hydrocarbyl group may contain one or moreheteroatoms. Preferably, said hydrocarbyl group has from 1 to 20 carbonatoms, more preferably from 1 to 12 carbon atoms, even more preferablyfrom 1 to 6 carbon atoms. For example, R⁸ may be C1-4 alkyl, preferablymethyl or ethyl

Non-limiting examples of suitable silane-compounds includetetramethoxysilane (TMOS or tetramethyl orthosilicate),tetraethoxysilane (TEOS or tetraethyl orthosilicate), methyltrimethoxysilane, methyl triethoxysilane, methyl tripropoxysilane,methyl tributoxysilane, ethyl trimethoxysilane, ethyl triethoxysilane,ethyl tripropoxysilane, ethyl tributoxysilane, n-propyltrimethoxysilane, n-propyl triethoxysilane, n-propyl tripropoxysilane,n-propyl tributoxysilane, isopropyl trimethoxysilane, isopropyltriethoxysilane, isopropyl tripropoxysilane, isopropyl tributoxysilane,phenyl trimethoxysilane, phenyl triethoxysilane, phenyltripropoxysilane, phenyl tributoxysilane, cyclopentyl trimethoxysilane,cyclopentyl triethoxysilane, diethylamino triethoxysilane, dimethyldimethoxysilane, dimethyl diethoxysilane, dimethyl dipropoxysilane,dimethyl dibutoxysilane, diethyl dimethoxysilane, diethyldiethoxysilane, diethyl dipropoxysilane, diethyl dibutoxysilane,di-n-propyl dimethoxysilane, d-n-propyl diethoxysilane, di-n-propyldipropoxysilane, di-n-propyl dibutoxysilane, diisopropyldimethoxysilane, diisopropyl diethoxysilane, diisopropyldipropoxysilane, diisopropyl dibutoxysilane, diphenyl dimethoxysilane,diphenyl diethoxysilane, diphenyl dipropoxysilane, diphenyldibutoxysilane, dicyclopentyl dimethoxysilane, dicyclopentyldiethoxysilane, diethyl diphenoxysilane, di-tert-butyl dimethoxysilane,methyl cyclohexyl dimethoxysilane, ethyl cyclohexyl dimethoxysilane,isobutyl isopropyl dimethoxysilane, tert-butyl isopropyldimethoxysilane, trifluoropropyl methyl dimethoxysilane,bis(perhydroisoquinolino) dimethoxysilane, dicyclohexyl dimethoxysilane,dinorbornyl dimethoxysilane, cyclopentyl pyrrolidino dimethoxysilane andbis(pyrrolidino) dimethoxysilane.

In an embodiment, the silane-compound for the additional external donoris dicyclopentyl dimethoxysilane, di-isopropyl dimethoxysilane,di-isobutyl dimethyoxysilane, methylcyclohexyl dimethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, dimethylaminotriethoxysilane, and one or more combinations thereof.

The invention also relates to a process to make the catalyst system bycontacting a Ziegler-Natta type procatalyst, a co-catalyst and anexternal electron donor. The procatalyst, the cocatalyst and theexternal donor can be contacted in any way known to the skilled personin the art; and as also described herein, more specifically as in theExamples.

The invention further relates to a process for making a polyolefin bycontacting an olefin with the catalyst system according to the presentinvention. The procatalyst, the cocatalyst, the external donor and theolefin can be contacted in any way known to the skilled person in theart; and as also described herein.

For instance, the external donor in the catalyst system according to thepresent invention can be complexed with the co-catalyst and mixed withthe procatalyst (pre-mix) prior to contact between the procatalyst andthe olefin. The external donor can also be added independently to thepolymerization reactor. The procatalyst, the co-catalyst, and theexternal donor can be mixed or otherwise combined prior to addition tothe polymerization reactor.

Contacting the olefin with the catalyst system according to the presentinvention can be done under standard polymerization conditions, known tothe skilled person in the art. See for example Pasquini, N. (ed.)“Polypropylene handbook” 2^(nd) edition, Carl Hanser Verlag Munich,2005. Chapter 6.2 and references cited therein.

The polymerization process may be a gas phase, a slurry or a bulkpolymerization process, operating in one or more than one reactor. Oneor more olefin monomers can be introduced in a polymerization reactor toreact with the procatalyst and to form an olefin-based polymer (or afluidized bed of polymer particles).

In the case of polymerization in a slurry (liquid phase), a dispersingagent is present. Suitable dispersing agents include for examplepropane, n-butane, isobutane, n-pentane, isopentane, hexane (e.g. iso-orn-), heptane (e.g. iso-or n-), octane, cyclohexane, benzene, toluene,xylene, liquid propylene and/or mixtures thereof. The polymerizationsuch as for example the polymerization temperature and time, monomerpressure, avoidance of contamination of catalyst, choice ofpolymerization medium in slurry processes, the use of furtheringredients (like hydrogen) to control polymer molar mass, and otherconditions are well known to persons of skill in the art. Thepolymerization temperature may vary within wide limits and is, forexample for propylene polymerization, from 0° C. to 120° C., preferablyfrom 40° C. to 100° C. The pressure during (propylene)(co)polymerization is for instance from 0.1 to 6 MPa, preferably from 1to 4 MPa.

Several types of polyolefins are prepared such as homopolyolefins,random copolymers and heterophasic polyolefin. The for latter, andespecially heterophasic polypropylene, the following is observed.

Heterophasic propylene copolymers are generally prepared in one or morereactors, by polymerization of propylene and optionally one or moreother olefins, for example ethylene, in the presence of a catalyst andsubsequent polymerization of a propylene-α-olefin mixture. The resultingpolymeric materials can show multiplpe phases (depending on monomerratio), but the specific morphology usually depends on the preparationmethod and monomer ratio. The heterophasic propylene copolymers employedin the process according to present invention can be produced using anyconventional technique known to the skilled person, for examplemultistage process polymerization, such as bulk polymerization, gasphase polymerization, slurry polymerization, solution polymerization orany combinations thereof. Any conventional catalyst systems, forexample, Ziegler-Natta or metallocene may be used. Such techniques andcatalysts are described, for example, in WO06/010414; Polypropylene andother Polyolefins, by Ser van der Ven, Studies in Polymer Science 7,Elsevier 1990; WO06/010414, U.S. Pat. Nos. 4,399,054 and 4,472,524.

The molar mass of the polyolefin obtained during the polymerization canbe controlled by adding hydrogen or any other agent known to be suitablefor the purpose during the polymerization. The polymerization can becarried out in a continuous mode or batch-wise. Slurry-, bulk-, andgas-phase polymerization processes, multistage processes of each ofthese types of polymerization processes, or combinations of thedifferent types of polymerization processes in a multistage process arecontemplated herein. Preferably, the polymerization process is a singlestage gas phase process or a multistage, for instance a two-stage gasphase process, e.g. wherein in each stage a gas-phase process is used orincluding a separate (small) prepolymerization reactor.

Examples of gas-phase polymerization processes include both stirred bedreactors and fluidized bed reactor systems; such processes are wellknown in the art. Typical gas phase olefin polymerization reactorsystems typically comprise a reactor vessel to which an olefinmonomer(s) and a catalyst system can be added and which contain anagitated bed of growing polymer particles. Preferably, thepolymerization process is a single stage gas phase process or amultistage, for instance a 2-stage, gas phase process wherein in eachstage a gas-phase process is used.

As used herein, “gas phase polymerization” is the way of an ascendingfluidizing medium, the fluidizing medium containing one or moremonomers, in the presence of a catalyst through a fluidized bed ofpolymer particles maintained in a fluidized state by the fluidizingmedium optionally assisted by mechanical agitation. Examples of gasphase polymerization are fluid bed, horizontal stirred bed and verticalstirred bed.

“fluid-bed,” “fluidized,” or “fluidizing” is a gas-solid contactingprocess in which a bed of finely divided polymer particles is elevatedand agitated by a rising stream of gas optionally assisted by mechanicalstirring. In a “stirred bed” upwards gas velocity is lower than thefluidization threshold.

A typical gas-phase polymerization reactor (or gas phase reactor)include a vessel (i.e., the reactor), the fluidized bed, a productdischarge system and may include a mechanical stirrer, a distributionplate, inlet and outlet piping, a compressor, a cycle gas cooler or heatexchanger. The vessel may include a reaction zone and may include avelocity reduction zone, which is located above the reaction zone (viz.bed). The fluidizing medium may include propylene gas and at least oneother gas such as an olefin and/or a carrier gas such as hydrogen ornitrogen. The contacting can occur by way of feeding the procatalystinto the polymerization reactor and introducing the olefin into thepolymerization reactor. In an embodiment, the process includescontacting the olefin with a co-catalyst. The co-catalyst can be mixedwith the procatalyst (pre-mix) prior to the introduction of theprocatalyst into the polymerization reactor. The co-catalyst may be alsoadded to the polymerization reactor independently of the procatalyst.The independent introduction of the co-catalyst into the polymerizationreactor can occur (substantially) simultaneously with the procatalystfeed. An external donor may also be present during the polymerizationprocess.

The olefin according to the invention may be selected from mono- anddi-olefins containing from 2 to 40 carbon atoms. Suitable olefinmonomers include alpha-olefins, such as ethylene, propylene,alpha-olefins having from 4 to 20 carbon atoms (viz. C4-20), such as1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene,1-decene, 1-dodecene and the like; C4-C20 diolefins, such as1,3-butadiene, 1,3-pentadiene, norbornadiene, 5-vinyl-2-norbornene(VNB), 1,4-hexadiene, 5-ethylidene-2-norbornene (ENB) anddicyclopentadiene; vinyl aromatic compounds having from 8 to 40 carbonatoms (viz. C8-C40) including styrene, o-, m- and p-methylstyrene,divinylbenzene, vinylbiphenyl, vinylnapthalene; and halogen-substitutedC8-C40 vinyl aromatic compounds such as chlorostyrene and fluorostyrene.

Preferably, the olefin is propylene or a mixture of propylene andethylene, to result in a propylene-based polymer, such as propylenehomopolymer or propylene-olefin copolymer. The olefin may analpha-olefin having up to 10 carbon atoms, such as ethylene, butane,hexane, heptane, octene. A propylene copolymer is herein meant toinclude both so-called random copolymers which typically have relativelylow comonomer content, e.g. up to 10 mol %, as well as so-called impactPP copolymers or heterophasic PP copolymers comprising higher comonomercontents, e.g. from 5 to 80 mol %, more typically from 10 to 60 mol %.The impact PP copolymers are actually blends of different propylenepolymers; such copolymers can be made in one or two reactors and can beblends of a first component of low comonomer content and highcrystallinity, and a second component of high comonomer content havinglow crystallinity or even rubbery properties. Such random and impactcopolymers are well-known to the skilled in the art. Apropylene-ethylene random copolymer may be produced in one reactor.Impact PP copolymers may be produced in two reactors: polypropylenehomopolymer may be produced in a first reactor; the content of the firstreactor is subsequently transferred to a second reactor into whichethylene (and optionally propylene) is introduced. This results inproduction of a propylene-ethylene copolymer (i.e. an impact copolymer)in the second reactor.

The present invention also relates to a polyolefin, preferably apolypropylene obtained or obtainable by a process, comprising contactingan olefin, preferably propylene or a mixture of propylene and ethylenewith the procatalyst according to the present invention. The termspolypropylene and propylene-based polymer are used hereininterchangeable. The polypropylene may be a propylene homopolymer or amixture of propylene and ethylene, such as a propylene-based copolymer,e.g. heterophasic propylene-olefin copolymer; random propylene-olefincopolymer, preferably the olefin in the propylene-based copolymers beinga C2, or C4-C6 olefin, such as ethylene, butylene, pentene or hexene.Such propylene-based (co)polymers are known to the skilled person in theart; they are also described herein above.

The present invention also relates to a polyolefin, preferably apropylene-based polymer obtained or obtainable by a process as describedherein above, comprising contacting propylene or a mixture of propyleneand ethylene with a catalyst system according to the present invention.

In one embodiment the present invention relates to the production of ahomopolymer of polypropylene.

Several polymer properties are discussed here.

Xylene soluble fraction (XS) is preferably from about 0.5 wt % to about10 wt %, or from about 1 wt % to about 8 wt %, or from 2 to 6 wt %, orfrom about 1 wt % to about 5 wt %. Preferably, the xylene amount (XS) islower than 7 wt %, preferably lower than 6 wt %, more preferably lowerthan 5 wt % or even lower than 4 wt % and most preferably lower than 3wt %.

The production rate is preferably from about 1 kg/g/hr to about 100kg/g/hr, or from about 5 kg/g/hr to about 20 kg/g/hr.

MFR is preferably from about 0.01 g/10 min to about 2000 g/10 min, orfrom about 0.01 g/10 min to about 1000 g/10 min; or from about 0.1 g/10min to about 500 g/10 min, or from about 0.5 g/10 min to about 150 g/10min, or from about 1 g/10 min to about 100 g/10 min.

The olefin polymer obtained in the present invention is considered to bea thermoplastic polymer. The thermoplastic polymer composition accordingto the invention may also contain one or more of usual additives, likethose mentioned above, including stabilisers, e.g. heat stabilisers,anti-oxidants, UV stabilizers; colorants, like pigments and dyes;clarifiers; surface tension modifiers; lubricants; flame-retardants;mould-release agents; flow improving agents; plasticizers; anti-staticagents; impact modifiers; blowing agents; fillers and reinforcingagents; and/or components that enhance interfacial bonding betweenpolymer and filler, such as a maleated polypropylene, in case thethermoplastic polymer is a polypropylene composition. The skilled personcan readily select any suitable combination of additives and additiveamounts without undue experimentation.

The amount of additives depends on their type and function; typically isof from 0 to about 30 wt %; preferably of from 0 to about 20 wt %; morepreferably of from 0 to about 10 wt % and most preferably of from 0 toabout 5 wt % based on the total composition. The sum of all componentsadded in a process to form the polyolefins, preferably thepropylene-base polymers or compositions thereof should add up to 100 wt%.

The thermoplastic polymer composition of the invention may be obtainedby mixing one or more of the thermoplastic polymers with one or moreadditives by using any suitable means. Preferably, the thermoplasticpolymer composition of the invention is made in a form that allows easyprocessing into a shaped article in a subsequent step, like in pellet orgranular form. The composition can be a mixture of different particlesor pellets; like a blend of a thermoplastic polymer and a master batchof nucleating agent composition, or a blend of pellets of athermoplastic polymer comprising one of the two nucleating agents and aparticulate comprising the other nucleating agent, possibly pellets of athermoplastic polymer comprising said other nucleating agent.Preferably, the thermoplastic polymer composition of the invention is inpellet or granular form as obtained by mixing all components in anapparatus like an extruder; the advantage being a composition withhomogeneous and well-defined concentrations of the nucleating agents(and other components).

The invention also relates to the use of the polyolefins, preferably thepropylene-based polymers (also called polypropylenes) according to theinvention in injection moulding, blow moulding, extrusion moulding,compression moulding, casting, thin-walled injection moulding, etc. forexample in food contact applications.

Furthermore, the invention relates to a shaped article comprising thepolyolefin, preferably the propylene-based polymer according to thepresent invention.

The polyolefin, preferably the propylene-based polymer according to thepresent invention may be transformed into shaped (semi)-finishedarticles using a variety of processing techniques. Examples of suitableprocessing techniques include injection moulding, injection compressionmoulding, thin wall injection moulding, extrusion, and extrusioncompression moulding. Injection moulding is widely used to producearticles such as for example caps and closures, batteries, pails,containers, automotive exterior parts like bumpers, automotive interiorparts like instrument panels, or automotive parts under the bonnet.Extrusion is for example widely used to produce articles, such as rods,sheets, films and pipes. Thin wall injection moulding may for example beused to make thin wall packaging applications both for food and non-foodsegments. This includes pails and containers and yellow fats/margarinetubs and dairy cups.

It is noted that the invention relates to all possible combinations offeatures recited in the claims. Features described in the descriptionmay further be combined.

Although the invention has been described in detail for purposes ofillustration, it is understood that such detail is solely for thatpurpose and variations can be made therein by those skilled in the artwithout departing from the spirit and scope of the invention as definedin the claims.

It is further noted that the invention relates to all possiblecombinations of features described herein, preferred in particular arethose combinations of features that are present in the claims.

It is further noted that the term ‘comprising’ does not exclude thepresence of other elements. However, it is also to be understood that adescription on a product comprising certain components also discloses aproduct consisting of these components. Similarly, it is also to beunderstood that a description on a process comprising certain steps alsodiscloses a process consisting of these steps.

EXAMPLES Example A

In a reaction vessel 2,4-pentandiol (10 gram) was added to a mixture ofpyridine (17 ml) and methylene dichloride (150 ml). The mixture wascooled to 10° C. and ethyl chloroformate (28 gram) was added drop wise.The mixture was further stirred overnight at 25° C. The completion ofreaction was monitored using gas chromatography. Then, an ammoniumchloride solution was added to the reaction mixture and phase separationinto an organic phase and an aqueous phase was allowed. The organiclayer is separated and obtained, washed with water, dried on anhydroussodium sulfate and distilled to give 22 gram of a crude product. Thecrude product was further purified by high vacuum distillation to give17.5 gram (74%) of diethyl pentane-2,4-diyl dicarbonate (I). The productwas characterized by: ¹H NMR(300 MHz CDCl₃) δ=1.29 (d, 6H); 1.37 (d,6H); 1.8 (m, 8H); 4.13 (m, 2H); 4.8 (m, 4H) (isomeric mixture). ¹³C NMR:δ=14.167, 20.029, 20.326, 41.726, 42.322, 63.599, 71.056, 71.041,71.811, 154.534, 154.580 (isomeric mixture). m/z 249.2 (m+1).

Example B

In a reaction vessel 2,4-pentandiol (10 gram) was added to a mixture ofpyridine (17 ml) and methylene dichloride (150 ml). The mixture wascooled to 10° C. and phenyl chloroformate (32 gram) was added drop wise.The mixture was further stirred overnight at 25° C. The completion ofreaction was monitored using Gas chromatography. Then, an ammoniumchloride solution was added to the reaction mixture and phase separationinto an organic phase and an aqueous phase was allowed. The organiclayer is separated and obtained, washed with water, dried on anhydroussodium sulfate and distilled to give 34 gram of a crude product. Thecrude product was further purified by high vacuum distillation to give23.8 gram (70%) of pentane-2,4-diyl diphenyl dicarbonate (II). Theproduct was characterized by: ¹H NMR(300 MHz CDCl₃) δ=1.37 (d, 2×CH₃););1.77 (d, —CH2); 4.13 (m, 2×CH); 7.29-7.42 (m, ArH) (isomeric mixture).

Comparative Example C Preparation of 4-[Benzoyl(Methyl)Amino]Pentan-2-yl Benzoate]

This compound is prepared as disclosed in the Examples WO2014001257.

Example 1

Step A) butyl Grignard Formation Step

This step was carried out as disclosed in Example 1.A ofWO2014/001257A1.

Step B) Preparation of the First Intermediate Reaction Product

This step was carried out as described in Example XX of EP 1 222 214 B1,except that the dosing temperature of the reactor was 35° C., the dosingtime was 360 min and the propeller stirrer was used. 250 ml of dibutylether was introduced to a 1 liter reactor. The reactor was fitted bypropeller stirrer and two baffles. The reactor was thermostated at 35°C.

The solution of reaction product of step A (360 ml, 0.468 mol Mg) and180 ml of a solution of tetraethoxysilane (TES) in dibutyl ether (DBE),(55 ml of TES and 125 ml of DBE), were cooled to 10° C., and then weredosed simultaneously to a mixing device of 0.45 ml volume supplied witha stirrer and jacket. Dosing time was 360 min. Thereafter the premixedreaction product A and the TES-solution were introduced to a reactor.The mixing device (mini-mixer) was cooled to 10° C. by means of coldwater circulating in the mini-mixer's jacket. The stirring speed in themini-mixer was 1000 rpm. The stirring speed in reactor was 350 rpm atthe beginning of dosing and was gradually increased up to 600 rpm at theend of dosing stage. On the dosing completion the reaction mixture washeated up to 60° C. and kept at this temperature for 1 hour. Then thestirring was stopped and the solid substance was allowed to settle. Thesupernatant was removed by decanting. The solid substance was washedthree times using 500 ml of heptane. As a result, a pale yellow solidsubstance, reaction product B (the solid first intermediate reactionproduct; the support), was obtained, suspended in 200 ml of heptane. Theaverage particle size of support was 22 μm and span value(d₉₀-d₁₀)/d₅₀=0.5.

Step C) Preparation of the Second Intermediate Reaction Product

Support activation was carried out as described in Example IV ofWO/2007/134851 to obtain the second intermediate reaction product.

In inert nitrogen atmosphere at 20° C. a 250 ml glass flask equippedwith a mechanical agitator is filled with slurry of 5 g of reactionproduct of step B dispersed in 60 ml of heptane. Subsequently a solutionof 0.22 ml ethanol (EtOH/Mg=0.1) in 20 ml heptane is dosed understirring during 1 hour. After keeping the reaction mixture at 20° C. for30 minutes, a solution of 0.79 ml titanium tetraethoxide (TET/Mg=0.1) in20 ml of heptane was added for 1 hour. The slurry was slowly allowed towarm up to 30° C. for 90 min and kept at that temperature for another 2hours. Finally the supernatant liquid is decanted from the solidreaction product (the second intermediate reaction product; activatedsupport) which was washed once with 90 ml of heptane at 30° C.

Step D) Preparation of the Catalyst Component

A reactor was brought under nitrogen and 125 ml of titaniumtetrachloride was added to it. The reactor was heated to 100° C. and asuspension, containing about 5.5 g of activated support (step C) in 15ml of heptane, was added to it under stirring. Then the temperature ofreaction mixture was increased to 110° C. for 10 min and 1.47 g theinternal donor prepared in Example A in a ID/Mg molar ratio of 0.15 in 3ml of chlorobenzene was added to reactor and the reaction mixture waskept at 115° C. for 105 min. Then the stirring was stopped and the solidsubstance was allowed to settle. The supernatant was removed bydecanting, after which the solid product was washed with chlorobenzene(125 ml) at 100° C. for 20 min. Then the washing solution was removed bydecanting, after which a mixture of titanium tetrachloride (62.5 ml) andchlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115°C. for 30 min, after which the solid substance was allowed to settle.The supernatant was removed by decanting, and the last treatment wasrepeated once again. The solid substance obtained was washed five timesusing 150 ml of heptane at 60° C., after which the catalyst component,suspended in heptane, was obtained.

Step E) Polymerization of Propylene

Polymerization of propylene was carried out in a stainless steel reactor(with a volume of 0.7 I) in heptane (300 ml) at a temperature of 70° C.,total pressure 0.7 MPa and hydrogen presence (55 ml) for 1 hour in thepresence of a catalyst system comprising the catalyst componentaccording to step D, triethylaluminium as co-catalyst andn-propyltrimethoxy-silane as external donor. The concentration of thecatalyst component was 0.033 g/I; the concentration of triethylaluminiumwas 4.0 mmol/l; the concentration of n-propyl-trimethoxysilane was 0.2mmol/I.

Example 2

Example 2 was carried out in the same way as Example 1, but thepreparation of the catalyst component in step D was performed asfollows.

Step D) Preparation of the Catalyst Component

A reactor was brought under nitrogen and 125 ml of titaniumtetrachloride was added to it. The reactor was heated to 90° C. and asuspension, containing about 5.5 g of activated support in 15 ml ofheptane, was added to it under stirring. The reaction mixture was keptat 90° C. for 10 min. Then add 0.866 g of ethyl acetate (EA/Mg=0.25mol). The reaction mixture was kept for 60 min (stage I of procatalystpreparation). Then the stirring was stopped and the solid substance wasallowed to settle. The supernatant was removed by decanting, after whichthe solid product was washed with chlorobenzene (125 ml) at 100° C. for20 min. Then the washing solution was removed by decanting, after whicha mixture of titanium tetrachloride (62.5 ml) and chlorobenzene (62.5ml) was added. The temperature of reaction mixture was increased to 115°C. and 0.49 g of the internal donor obtained in Example A (ID/Mg=0.05mol) in 2 ml of chlorobenzene was added to reactor.

Then the reaction mixture was kept at 115° C. for 30 min (stage II ofprocatalyst preparation). After which the stirring was stopped and thesolid substance was allowed to settle. The supernatant was removed bydecanting, after which a mixture of titanium tetrachloride (62.5 ml) andchlorobenzene (62.5 ml) was added. The reaction mixture was kept at 115°C. for 30 min (stage III of procatalyst preparation), after which thesolid substance was allowed to settle. The supernatant was removed bydecanting and the solid was washed five times using 150 ml of heptane at60° C., after which the catalyst component, suspended in heptane, wasobtained.

Example 3

Example 3 was carried out in the same way as Example 2, but the internaldonor according to Example B was used in an amount of 0.68 gram (0.05mol/mol ID/Mg).

Example 4

Example 4 was carried out in the same way as Example 2, but the internaldonor according to Example B was used in an amount of 1.36 gram (0.1mol/mol ID/Mg).

Example 5

Example 5 is a comparative example that was carried out in the same wayas disclosed in Example 1 of WO 2014/001257. Data on the catalystperformance at the propylene polymerization are presented in Table 1.

TABLE 1 PP Yield ID/ ME ID Ti Kg/g APP MFR Mw/ Ex. ID Mg ME Wt. % Wt. %Wt. % cat Wt. % XS % g/10 min Mn 1 Ex. A 0.15 — — 1.1 4.5 8.5 9.3 11.017.8 4.4 2 Ex. A 0.05 EA 1.0 2.4 3.5 9.3 2.9 7.0 20.5 5.0 3 Ex. B 0.05EA 0.7 2.5 3.0 4.3 7.1 13.7 13.3 4.6 4 Ex. B 0.1 EA 0.5 6.8 2.9 5.5 6.613.5 8.4 4.6 5 Comp. C 0.15 — — 17.9 2.4 4.4 0.9 2.5 0.6 7.7

Abbreviations and measuring methods:

-   -   ID/Mg is the molar ratio of the internal donor (ID) over        magnesium    -   ME wt. % is the amount of monoester in wt. % based on the total        amount of the catalyst composition    -   ID wt. % is the amount of internal donor in wt. % based on the        total amount of the procatalyst composition    -   Ti wt. % is the amount of titanium in wt. % based on the total        amount of the procatalyst composition    -   PP yield, in kg/g cat is the amount of polypropylene obtained        per gram of procatalyst.    -   APP, wt % is the weight percentage of atactic polypropylene.        Atactic PP is the PP fraction soluble in heptane during        polymerization. APP was determined as follows: 100 ml of the        filtrate (y ml) obtained in separating the polypropylene powder        (x g) and the heptane was dried over a steam bath and then under        vacuum at 60° C. That yielded z g of atactic PP. The total        amount of Atactic PP (q g) is: (y/100)*z. The weight percentage        of Atactic PP is: (q/(q+x))*100%.    -   XS, wt % is xylene solubles, measured according to ASTM D        5492-10.    -   MFR is the melt flow rate as measured at 230° C. with 2.16 kg        load, measured according to ISO 1133:2005.    -   Mw/Mn: Polymer molecular weight and its distribution (MWD) were        determined by Waters 150° C. gel permeation chromatograph        combined with a Viscotek 100 differential viscosimeter. The        chromatograms were run at 140° C. using 1,2,4-trichlorobenzene        as a solvent with a flow rate of 1 ml/min. The refractive index        detector was used to collect the signal for molecular weights.    -   ¹H-NMR and ¹³C-NMR spectra were recorded on a Varian Mercury-300        MHz NMR Spectrometer, using deuterated chloroform as a solvent.

From the Examples above it is clear that using a internal donoraccording to the present invention will lead to polyolefins having amoderate MWD and a high hydrogen sensitivity.

When comparing the internal donor according to Example A and B, thefollowing is observed. When using the internal donor according toExample A (ethyl as R⁹³), the activity is noticeably higher, the APP andXS are less and the MFR is higher

Hence one or more of the objections of the present invention areobtained by using an internal donor according to Formula A.

The invention claimed is:
 1. A procatalyst for polymerization ofolefins, which comprises the compound represented by Formula A, as aninternal electron donor,

wherein: R₉₄, R₉₅, R₉₆, R₉₇, R₉₈, and R₉₉ are each independentlyselected from hydrogen or a linear, branched or cyclic hydrocarbyl groupselected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, andone or more combinations thereof; each R₉₃ group is independently arylhaving 6 to 20 carbon atoms.
 2. The procatalyst according to claim 1,wherein R₉₄, R₉₅, R₉₆,R₉₇, R₉₈, and R₉₉ are independently selected froma group consisting of hydrogen, C₁-C₁₀ straight and branched alkyl;C₃-C₁₀ cycloalkyl; C₆-C₁₀ aryl; and C₇-C₁₀ alkaryl and aralkyl group. 3.A procatalyst for polymerization of olefins, which comprises thecompound represented by Formula A, as an internal electron donor,

wherein R₉₄ and R₉₅ is each a hydrogen atom and R₉₆, R₉₇, R₉₈, and R₉₉are independently selected from a group consisting of C₁-C₁₀ straightand branched alkyl; C₃-C₁₀ cycloalkyl; C₆-C₁₀ aryl; and C₇-C₁₀ alkaryland aralkyl group; and each R₉₃ group is independently a linear,branched or cyclic hydrocarbyl group selected from alkyl, alkenyl, aryl,aralkyl, or alkylaryl groups, and one or more combinations thereof. 4.The procatalyst according to claim 1, wherein R₉₄ and R₉₅ is each ahydrogen atom, and when one of R₉₆ and R₉₇ and one of R₉₈ and R₉₉ has atleast one carbon atom, then the other one of R₉₆ and R₉₇ and of R₉₈ andR₉₉ is each a hydrogen atom.
 5. The procatalyst according to claim 1,wherein each of the R₉₃ has 6 to 12 carbon atoms.
 6. A procatalyst forpolymerization of olefins, which comprises an internal electron donor,wherein the internal electron donor is pentane-2,4-diyl diphenyldicarbonate:


7. A process for preparing the procatalyst according to claim 1,comprising contacting a magnesium-containing support with ahalogen-containing titanium compound and an internal electron donor,wherein the internal electron donor is represented by Formula A,

wherein: R₉₄, R₉₅, R₉₆, R₉₇, R₉₈, and R₉₉ are each independentlyselected from hydrogen or a linear, branched or cyclic hydrocarbyl groupselected from alkyl, alkenyl, aryl, aralkyl, or alkylaryl groups, andone or more combinations thereof; each R₉₃ group is independently arylhaving 6 to 20 carbon atoms.
 8. The process according to claim 7, whichcomprises the steps of: i) contacting a compound R⁴ _(z),MgX⁴ _(2−z)with an alkoxy- or aryloxy-containing silane compound to give a firstintermediate reaction product, being a solid Mg(OR¹)_(x)X¹ _(2−x),wherein: R⁴ is the same as R¹ being a linear, branched or cyclichydrocarbyl group independently selected from alkyl, alkenyl, aryl,aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof, wherein said hydrocarbyl group may be substitutedor unsubstituted, may contain one or more heteroatoms; X⁴ and X¹ areeach independently selected from the group of consisting of fluoride(F—), chloride (Cl—), bromide (Br—) or iodide (I—); z is in a range oflarger than 0 and smaller than 2, being 0<z<2; ii) optionally contactingthe solid Mg(OR¹)_(x)X¹ _(2−x) obtained in step ii) with at least oneactivating compound selected from the group formed by activatingelectron donors and metal alkoxide compounds of formulaM¹(OR²)_(v−w)(OR³)_(w) or M²(OR²)_(v−w)(R³)_(w), to obtain a secondintermediate product; wherein: M¹ is a metal selected from the groupconsisting of Ti, Zr, Hf, Al or Si; v is the valency of M⁴; M² is ametal being Si; v is the valency of M²; R² and R³ are each a linear,branched or cyclic hydrocarbyl group independently selected from alkyl,alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one ormore combinations thereof, wherein said hydrocarbyl group may besubstituted or unsubstituted, may contain one or more heteroatoms, vbeing either 3 or 4 and w is smaller than v; and iii) contacting thefirst or second intermediate reaction product, obtained respectively instep i) or ii), with a halogen-containing Ti-compound and said internalelectron donor represented by a compound of Formula A.
 9. The processaccording to claim 7, wherein step iii further comprises contacting thefirst or second intermediate reaction product with an activator,selected from the group consisting of benzamides, alkylbenzoates, andmono-esters.
 10. A polymerization catalyst system comprising theprocatalyst according to claim 1, a co-catalyst and optionally anexternal electron donor.
 11. A process of making a polyolefin bycontacting an olefin with the catalyst system according to claim
 10. 12.A method for the polymerization of an olefin, comprising: polymerizingthe olefin using of the compound represented by Formula A, as aninternal electron donor in a procatalyst for the polymerization of anolefin,

wherein: R₉₄, R₉₅, R₉₆, R₉₇, R₉₈, and R₉₉ are the same or different andare independently selected from a group consisting of hydrogen straight,branched and cyclic alkyl and aromatic substituted and unsubstitutedhydrocarbyl having 1 to 20 carbon atoms; each R₉₃ group is independentlyaryl having 6 to 20 carbon atoms.
 13. The method according to claim 12,wherein each of R₉₃ is independently selected from the group consistingof aryl having 6 to 12 carbon atoms.
 14. The method according to claim12, wherein R₉₄ and R₉₅ is each a hydrogen atom and R₉₆, R₉₇, R₉₈, andR₉₉ are independently selected from a group consisting of C₁-C₁₀straight and branched alkyl; C₃-C₁₀ cycloalkyl; C₆-C₁₀ aryl; and C₇-C₁₀alkaryl and aralkyl group.
 15. The method according to claim 12, whereinthe internal electron donor is pentane-2,4-diyl diphenyl dicarbonate:


16. The procatalyst according to claim 3, wherein each of R₉₃ isindependently selected from the group consisting of aryl having 6 to 12carbon atoms.
 17. The procatalyst according to claim 6, wherein each ofR₉₃ is independently selected from the group consisting of aryl having 6to 12 carbon atoms.
 18. The procatalyst according to claim 1, whereinthe internal electron donor is pentane-2,4-diyl diphenyl dicarbonate:


19. The procatalyst according to claim 1, wherein R₉₄ and R₉₅ is each ahydrogen atom and R₉₆, R₉₇, R₉₈, and R₉₉ are independently selected froma group consisting of C₁-C₁₀ straight and branched alkyl; C₃-C₁₀cycloalkyl; C₆-C₁₀ aryl; and C₇-C₁₀ alkaryl and aralkyl group.
 20. Theprocatalyst according to claim 3, wherein R₉₆, R₉₇, R₉₈, and R₉₉ areindependently selected from C₁-C₁₀ straight and branched alkyl groups.21. A process for preparing the procatalyst according to claim 1,comprising contacting a magnesium-containing support with ahalogen-containing titanium compound and an internal electron donor,wherein the internal electron donor is represented by a compoundaccording to Formula A,

wherein R₉₄ and R₉₅ is each a hydrogen atom, and when one of R₉₆ and R₉₇and one of R₉₈ and R₉₉ has at least one carbon atom, then the other oneof R₉₆ and R₉₇ and of R₉₈ and R₉₉ is each a hydrogen atom; which processcomprises the steps of: i) contacting a compound R⁴ _(z)MgX⁴ _(2−z),with an alkoxy- or aryloxy-containing silane compound to give a firstintermediate reaction product, being a solid Mg(OR¹)_(x)X¹ _(2−x),wherein: R⁴ is the same as R¹ being a linear, branched or cyclichydrocarbyl group independently selected from alkyl, alkenyl, aryl,aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof; wherein said hydrocarbyl group may be substitutedor unsubstituted, may contain one or more heteroatoms; X⁴ and X¹ areeach independently selected from the group of consisting of fluoride(F—), chloride (Cl—), bromide (Br—) or iodide (I—); z is in a range oflarger than 0 and smaller than 2, being 0<z<2; ii) optionally contactingthe solid Mg(OR¹)_(x)X¹ _(2−x) obtained in step ii) with at least oneactivating compound selected from the group formed by activatingelectron donors and metal alkoxide compounds of formulaM¹(OR²)_(v−w)(OR³)_(w) or M²(OR²)_(v−w)(R³)_(w), to obtain a secondintermediate product; wherein: M¹ is a metal selected from the groupconsisting of Ti, Zr, Hf, Al or Si; v is the valency of M¹; M² is ametal being Si; v is the valency of M²; R² and R³ are each a linear,branched or cyclic hydrocarbyl group independently selected from alkyl,alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one ormore combinations thereof, wherein said hydrocarbyl group may besubstituted or unsubstituted, may contain one or more heteroatoms, vbeing either 3 or 4 and w is smaller than v; and iii) contacting thefirst or second intermediate reaction product, obtained respectively instep i) or ii), with a halogen-containing Ti-compound and said internalelectron donor represented by a compound of Formula A.
 22. A process forpreparing the procatalyst according to claim 21, wherein one of R₉₆ andR₉₇ and one of R₉₈ and R₉₉ is selected from the group consisting ofC₁-C₁₀ straight and branched alkyl.
 23. A process for preparing theprocatalyst according to claim 1, comprising contacting amagnesium-containing support with a halogen-containing titanium compoundand an internal electron donor, wherein the internal electron donor isrepresented by a compound according to Formula A, being diethylpentane-2,4-diyl dicarbonate:

which process comprises: i) contacting a compound R⁴ _(z)MgX⁴ _(2−z),with an alkoxy- or aryloxy-containing silane compound to give a firstintermediate reaction product, being a solid Mg(OR¹)_(x)X¹ _(2−x),wherein: R⁴ is the same as R¹ being a linear, branched or cyclichydrocarbyl group independently selected from alkyl, alkenyl, aryl,aralkyl, alkoxycarbonyl or alkylaryl groups, and one or morecombinations thereof; wherein said hydrocarbyl group may be substitutedor unsubstituted, may contain one or more heteroatoms; X⁴ and X¹ areeach independently selected from the group of consisting of fluoride(F—), chloride (Cl—), bromide (Br—) or iodide (I—); z is in a range oflarger than 0 and smaller than 2, being 0<z<2; ii) optionally contactingthe solid Mg(OR¹)_(x)X¹ _(2−x) obtained in step ii) with at least oneactivating compound selected from the group formed by activatingelectron donors and metal alkoxide compounds of formulaM¹(OR²)_(v−w)(OR³)_(w), or M²(OR²)_(v−w)(R³)_(w), to obtain a secondintermediate product; wherein: M¹ is a metal selected from the groupconsisting of Ti, Zr, Hf, Al or Si; v is the valency of M¹; M² is ametal being Si; v is the valency of M²; R² and R³ are each a linear,branched or cyclic hydrocarbyl group independently selected from alkyl,alkenyl, aryl, aralkyl, alkoxycarbonyl or alkylaryl groups, and one ormore combinations thereof; wherein said hydrocarbyl group may besubstituted or unsubstituted, may contain one or more heteroatoms, vbeing either 3 or 4 and w is smaller than v; and iii) contacting thefirst or second intermediate reaction product, obtained respectively instep i) or ii), with a halogen-containing Ti-compound and said internalelectron donor represented by a compound of Formula A.